Table of Contents
IX
Volume 1:
Compounds with Transition Metal±Carbon ð-Bonds
and Compounds of groups 10±8 (Ni, Pd, Pt, Co, Rh,
Ir, Fe, Ru, Os)
1.1
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
V
Table of Contents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
IX
Introduction
M. Lautens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1
Product Class 1: Organometallic Complexes of Nickel
J. Montgomery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
11
1.2
Product Class 2: Organometallic Complexes of Palladium
1.2.1
Product Subclass 1: Palladium±Diene Complexes
J. M. Takacs, X. Jiang, and S. Vayalakkada . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
63
Product Subclass 2: Palladium±Allyl Complexes
R. W. Friesen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
113
1.2.2
1.2.3
Product Subclass 3: Palladium±Alkyne Complexes
J. M. Takacs, S. Vayalakkada, and X. Jiang . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
1.2.4
Product Subclass 4: Palladium±Alkene Complexes
J. M. Takacs and S. Vayalakkada . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 319
1.3
Product Class 3: Organometallic Complexes of Platinum
A. Ogawa and T. Hirao . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
1.4
Product Class 4: Organometallic Complexes of Cobalt
M. Malacria, C. Aubert, and J.-L. Renaud . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 439
1.5
Product Class 5: Organometallic Complexes of Rhodium
I. Ojima, A. T. Vu, and D. Bonafoux . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 531
1.6
Product Class 6: Organometallic Complexes of Iridium
J. M. OConnor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 617
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© Georg Thieme Verlag KG
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Table of Contents
1.7
Product Class 7: Organometallic Complexes of Iron
1.7.1
Product Subclass 1: Iron±Arene Complexes
G. R. Stephenson . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
749
Product Subclass 2: Iron±Dienyl Complexes
G. R. Stephenson . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
755
Product Subclass 3: Iron±Diene Complexes
G. R. Stephenson . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
778
Product Subclass 4: Iron±Allyl Complexes
G. R. Stephenson . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
826
Product Subclass 5: Iron±Alkene Complexes
G. R. Stephenson . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
839
Product Subclass 6: Iron±Carbene Complexes
G. R. Stephenson . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
846
Product Subclass 7: Iron±Alkyl Complexes
G. R. Stephenson . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
853
Product Subclass 8: Ferrocenes
M. Perseghini and A. Togni . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
889
Product Class 8: Organometallic Complexes of Ruthenium
N. Chatani . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
931
Product Class 9: Organometallic Complexes of Osmium
J. Gonzalez and W. D. Harman . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
981
1.7.2
1.7.3
1.7.4
1.7.5
1.7.6
1.7.7
1.7.8
1.8
1.9
Keyword Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1017
Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1055
Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1107
Science of Synthesis Original Edition Volume 1
© Georg Thieme Verlag KG
XI
Table of Contents
Table of Contents
Introduction
M. Lautens
Introduction
............................................................
1
Product Class 1: Organometallic Complexes of Nickel
J. Montgomery
1.1
1.1
Product Class 1: Organometallic Complexes of Nickel . . . . . . . . . . . . . . . . . . . . .
11
1.1.1
Product Subclass 1: Nickel Complexes of 1,3-Dienes . . . . . . . . . . . . . . . . . . . . . .
12
Synthesis of Product Subclass 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
12
Ligand Exchange with Bis(ç -cycloocta-1,5-diene)nickel(0) . . .
12
Applications of Product Subclass 1 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . .
13
1.1.1.6
Method 2:
Method 3:
Method 4:
Variation 1:
Variation 2:
Method 5:
Method 6:
Diene±Diene Cycloadditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Diene±Alkyne Cycloadditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Diene±Aldehyde Reductive Cyclizations . . . . . . . . . . . . . . . . . . . . .
Triethylsilane-Mediated Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . .
Triethylborane-Mediated Reactions . . . . . . . . . . . . . . . . . . . . . . . . .
1,4-Dialkylation of Dienes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Hydrocyanation of Dienes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
13
14
15
15
16
16
17
1.1.2
Product Subclass 2: Nickel±Allyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
17
Synthesis of Product Subclass 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
17
Oxidative Addition of Nickel(0) with Allylic Electrophiles . . . . . .
Addition of Allylmagnesium Halides to Nickel(II) Salts . . . . . . . .
Oxidative Addition of Nickel(0) with Enones in
the Presence of Lewis Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
17
18
Applications of Product Subclass 2 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . .
21
1.1.1.1
1.1.1.2
1.1.1.3
1.1.1.4
1.1.1.4.1
1.1.1.4.2
1.1.1.5
Method 1:
1.1.2.3
Method 1:
Method 2:
Method 3:
1.1.2.4
Method 4:
1.1.2.1
1.1.2.2
1.1.2.5
Method 5:
1.1.2.6
Method 6:
1.1.2.7
Method 7:
1.1.2.7.1
Variation 1:
Variation 2:
Variation 3:
1.1.2.7.2
1.1.2.7.3
4
19
Oxidative Cyclization of Nickel(0) Complexes of
Conjugated Dienes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Coupling of Allyl Halide Derived Nickel±Allyl Complexes
with Alkyl Halides and Other Electrophiles . . . . . . . . . . . . . . . . . . . 21
Coupling of Enal-Derived Nickel±Allyl Complexes
with Alkyl Halides and Other Electrophiles . . . . . . . . . . . . . . . . . . . 22
Coupling of Nickel±Allyl Complexes with
Main Group Organometallics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
Allylic Ether Derived ð-Allyl Complexes . . . . . . . . . . . . . . . . . . . . . . 24
Enal-Derived ð-Allyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
Allylic Alcohol Derived ð-Allyl Complexes . . . . . . . . . . . . . . . . . . . . 26
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1.1.2.8
1.1.2.10
Method 8:
Method 9:
Method 10:
1.1.3
Product Subclass 3: Nickel±Alkyne Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
1.1.2.9
Addition of Stabilized Nucleophiles to Nickel±Allyl Complexes
27
Alkyne Insertions with Nickel±Allyl Complexes . . . . . . . . . . . . . . . 27
Alkene Insertions with Nickel±Allyl Complexes . . . . . . . . . . . . . . . 29
Synthesis of Product Subclass 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
1.1.3.1
Method 1:
Ligand Exchange with Nickel±Alkene Complexes . . . . . . . . . . . . . 30
Applications of Product Subclass 3 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . .
31
Coupling of Alkynes with Carbon Dioxide . . . . . . . . . . . . . . . . . . . .
Coupling of Alkynes with Isocyanides . . . . . . . . . . . . . . . . . . . . . . .
Coupling of Alkynes with Aldehydes . . . . . . . . . . . . . . . . . . . . . . . . .
Coupling of Two Alkynes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Coupling of Alkynes with Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . .
[2 + 2 + 2] Cycloadditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Alkyne Carbonylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Alkyne Hydrocyanation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Alkyne Hydrosilylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Alkyne Carbozincation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
31
32
32
35
36
38
40
40
40
41
1.1.3.11
Method 2:
Method 3:
Method 4:
Method 5:
Method 6:
Method 7:
Method 8:
Method 9:
Method 10:
Method 11:
1.1.4
Product Subclass 4: Nickel±Alkene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
1.1.3.2
1.1.3.3
1.1.3.4
1.1.3.5
1.1.3.6
1.1.3.7
1.1.3.8
1.1.3.9
1.1.3.10
Synthesis of Product Subclass 4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
1.1.4.1
Method 1:
Ligand Exchange with Nickel(0) Complexes . . . . . . . . . . . . . . . . . . 42
Applications of Product Subclass 4 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . . 43
1.1.4.2
1.1.4.2.1
1.1.4.2.2
1.1.4.2.3
1.1.4.2.4
1.1.4.3
1.1.4.4
1.1.4.5
1.1.4.6
1.1.4.7
1.1.4.8
1.1.4.9
1.1.4.10
1.1.4.11
Method 2:
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Method 3:
Method 4:
Method 5:
Method 6:
Method 7:
Method 8:
Method 9:
Method 10:
Method 11:
Conjugate Addition to Electrophilic Double Bonds . . . . . . . . . . .
Organoaluminums . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Organozincs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Organozirconiums . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Direct Conjugate Addition of Alkyl Halides . . . . . . . . . . . . . . . . . . .
Coupling of Two Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Alkene Carbonylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Alkene Hydrocyanation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Alkene Hydrosilylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Alkene Hydroalumination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Alkene Hydrozincation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Alkene Carbozincation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Homo-Diels±Alder Cycloadditions . . . . . . . . . . . . . . . . . . . . . . . . . . .
Alkene Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Science of Synthesis Original Edition Volume 1
© Georg Thieme Verlag KG
43
43
44
46
47
48
51
52
53
53
55
56
57
57
Table of Contents
1.2
Product Class 2: Organometallic Complexes of Palladium
1.2.1
Product Subclass 1: Palladium±Diene Complexes
J. M. Takacs, X. Jiang, and S. Vayalakkada
1.2.1
1.2.1.1
Product Subclass 1: Palladium±Diene Complexes . . . . . . . . . . . . . . . . . . . . . . . .
63
Synthesis of Product Subclass 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
64
Method 1:
Preparation and Characterization of
Palladium±Diene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
64
Applications of Product Subclass 1 in Organic Synthesis . . . . . . . . . . . . . . . . . . . .
65
1,3-Dienes: The 1,4-Addition of Nucleophiles . . . . . . . . . . . . . . .
The Oxidative Addition of Carbon Nucleophiles . . . . . . . . . . . . .
The Reductive Addition of Carbon Nucleophiles . . . . . . . . . . . . .
The Oxidative Addition of Oxygen Nucleophiles . . . . . . . . . . . . .
The Reductive Addition of Oxygen Nucleophiles . . . . . . . . . . . .
The Addition of Nitrogen Nucleophiles . . . . . . . . . . . . . . . . . . . . .
The Reductive Addition of Sulfur Nucleophiles . . . . . . . . . . . . . .
The Oxidative Carbonylation of 1,3-Dienes . . . . . . . . . . . . . . . . .
The Reductive Carbonylation of 1,3-Dienes . . . . . . . . . . . . . . . . .
Allenes: The Addition of Nucleophiles . . . . . . . . . . . . . . . . . . . . . .
The Addition of Carbon and Hydrogen Across the Allene . . . .
The Addition of Carbon and Silicon Across the Allene . . . . . . . .
65
67
69
70
77
78
79
80
81
82
83
88
1.2.1.3.3
Method 2:
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Variation 5:
Variation 6:
Variation 7:
Variation 8:
Method 3:
Variation 1:
Variation 2:
Variation 3:
1.2.1.3.4
Variation 4:
1.2.1.3.5
Variation 5:
1.2.1.3.6
Variation 6:
1.2.2
Product Subclass 2: Palladium±Allyl Complexes
R. W. Friesen
1.2.1.2
1.2.1.2.1
1.2.1.2.2
1.2.1.2.3
1.2.1.2.4
1.2.1.2.5
1.2.1.2.6
1.2.1.2.7
1.2.1.2.8
1.2.1.3
1.2.1.3.1
1.2.1.3.2
1.2.2
1.2.2.1
1.2.2.1.1
1.2.2.1.2
1.2.2.1.3
1.2.2.1.4
XIII
The Addition of Heteroatoms (i.e., O, N, S, or Se)
and Hydrogen Across the Allene . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
The Addition of the Oxygen, Nitrogen,
or Carbon and Carbon Moiety Across the Allene . . . . . . . . . . . . 93
The Addition of the Oxygen or Nitrogen and Halogen Moiety
Across the Allene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
The Addition of the Oxygen, Nitrogen, or Carbon and
Carbon Moiety via the Insertion of Carbon Monoxide or
an Alkene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
Product Subclass 2: Palladium±Allyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . .
113
Synthesis of Product Subclass 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
115
Transmetalation with Allyl Organometallics . . . . . . . . . . . . . . . . .
From Allylsilanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From Allylstannanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From Allylmercurials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From Allyl Grignard Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
115
115
116
117
118
Method 1:
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Science of Synthesis Original Edition Volume 1
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Table of Contents
1.2.2.2
Method 2:
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Method 3:
Method 4:
Variation 1:
Variation 2:
Method 5:
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Variation 5:
Variation 6:
Method 6:
Variation 1:
Variation 2:
Method 7:
Method 8:
Variation 1:
Variation 2:
Variation 3:
Method 9:
Variation 1:
Variation 2:
Method 10:
1.2.2.2.1
1.2.2.2.2
1.2.2.2.3
1.2.2.2.4
1.2.2.3
1.2.2.4
1.2.2.4.1
1.2.2.4.2
1.2.2.5
1.2.2.5.1
1.2.2.5.2
1.2.2.5.3
1.2.2.5.4
1.2.2.5.5
1.2.2.5.6
1.2.2.6
1.2.2.6.1
1.2.2.6.2
1.2.2.7
1.2.2.8
1.2.2.8.1
1.2.2.8.2
1.2.2.8.3
1.2.2.9
1.2.2.9.1
1.2.2.9.2
1.2.2.10
From Allylic Hydrogen Abstraction of Alkenes . . . . . . . . . . . . . . .
Palladation of Unsaturated Esters . . . . . . . . . . . . . . . . . . . . . . . . . .
Palladation of â-Oxo Esters and Diketene . . . . . . . . . . . . . . . . . . .
Palladation of Unsaturated Ketones . . . . . . . . . . . . . . . . . . . . . . . .
Palladation of Unactivated Alkenes . . . . . . . . . . . . . . . . . . . . . . . . .
Bridge Splitting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Palladation of 1,2-Dienes (Allenes) . . . . . . . . . . . . . . . . . . . . . . . . .
From Reaction of Allenes and Palladium Salts . . . . . . . . . . . . . . .
Insertion of Allenes into Allylpalladium Complexes . . . . . . . . . .
Palladation of 1,3- and 1,4-Dienes . . . . . . . . . . . . . . . . . . . . . . . . . .
Hydropalladation of 1,3-Dienes . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Heteropalladation of 1,3-Dienes . . . . . . . . . . . . . . . . . . . . . . . . . . .
Methoxypalladation of Cyclic 1,4-Dienes . . . . . . . . . . . . . . . . . . .
Insertion of 1,3-Dienes into Allylpalladium Complexes . . . . . .
Palladation of Dienol Silyl Ethers . . . . . . . . . . . . . . . . . . . . . . . . . . .
Reaction of Dienes and Organomercurials with Palladium Salts
From Reaction of Allyl and Benzyl Halides . . . . . . . . . . . . . . . . . .
From Reaction with Allyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . .
From Reaction with Benzyl Halides . . . . . . . . . . . . . . . . . . . . . . . . .
Insertion of Palladium(0) into Allyloxy Derivatives . . . . . . . . . . .
Palladation of Cyclopropane Derivatives . . . . . . . . . . . . . . . . . . . .
From Vinylcyclopropanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From Methylenecyclopropanes . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From Cyclopropenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Palladative Coupling of Vinyl Organometallics with Alkenes
Vinylpalladation of Alkenes Using Vinylmercurials . . . . . . . . . . .
Palladative Dimerization of Vinylsilanes . . . . . . . . . . . . . . . . . . . .
Ligand Metathesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
118
118
119
120
121
128
129
129
131
132
132
133
138
139
140
141
142
142
145
146
147
147
149
150
151
151
152
153
Applications of Product Subclass 2 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 154
1.2.2.11
Method 11:
1.2.2.12
Method 12:
Variation 1:
Variation 2:
1.2.2.12.1
1.2.2.12.2
1.2.2.15.2
Variation 3:
Method 13:
Method 14:
Method 15:
Variation 1:
Variation 2:
1.2.2.16
Method 16:
1.2.2.17
Method 17:
1.2.2.12.3
1.2.2.13
1.2.2.14
1.2.2.15
1.2.2.15.1
Allylsilanes from Reaction of Allylpalladium Complexes
and Disilanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
Allylsilanes from Allylic Esters and Chlorides . . . . . . . . . . . . . . . . 158
Via Reaction with (Trialkylsilyl)aluminum Reagents . . . . . . . . . . 158
Via Palladium-Catalyzed Electroreductive Cleavage and
Reaction with Trialkylchlorosilanes . . . . . . . . . . . . . . . . . . . . . . . . . 159
Via Reaction with Disilanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
Allylsilanes from Reduction of Allylic Carbonates . . . . . . . . . . . . 162
Allylsilanes from Hydrosilylation of 1,3-Dienes with Silanes . . 162
Allylstannanes from Allylic Acetates and Phosphates . . . . . . . . 163
Via Reaction with Trialkylstannylaluminates . . . . . . . . . . . . . . . . . 163
Via Reaction with Trialkylchlorostannane and
Samarium(II) Iodide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
Allylmercurials from Reaction of Allylpalladium Complexes
and Metallic Mercury . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
á,â-Unsaturated Esters from Dehydrogenation of
Saturated Esters via Their Ketene Silyl Acetals . . . . . . . . . . . . . . 166
Science of Synthesis Original Edition Volume 1
© Georg Thieme Verlag KG
Table of Contents
1.2.2.18
Method 18:
1.2.2.19
Method 19:
1.2.2.20
Method 20:
1.2.2.20.1
Variation 1:
Variation 2:
Variation 3:
Method 21:
1.2.2.20.2
1.2.2.20.3
1.2.2.21
1.2.2.24
Method 22:
Method 23:
Method 24:
1.2.2.25
Method 25:
1.2.2.22
1.2.2.23
1.2.2.26
Variation 1:
Variation 2:
Variation 3:
Method 26:
1.2.2.27
Method 27:
1.2.2.28
Method 28:
1.2.2.29
Method 29:
1.2.2.30
Method 30:
1.2.2.31
Method 31:
1.2.2.31.1
1.2.2.31.2
Variation 1:
Variation 2:
1.2.2.32
Method 32:
1.2.2.33
Method 33:
Variation 1:
1.2.2.25.1
1.2.2.25.2
1.2.2.25.3
1.2.2.33.1
1.2.2.33.2
1.2.2.34
1.2.2.35
Variation 2:
Method 34:
Method 35:
XV
á,â-Unsaturated Nitriles from Decarboxylation of
Allyl á-Cyanocarboxylates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
â,ã-Unsaturated Esters from Carbonylation of
Allylpalladium Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
â,ã-Unsaturated Esters from Carbonylation of
Allylic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Via Allylic Carbonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Via Allylic Esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Via Allylic Phosphates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
â,ã-Unsaturated Nitriles from Cyanation of
Allylic Carbonates and Acetates . . . . . . . . . . . . . . . . . . . . . . . . . . . .
ã,ä-Unsaturated Esters from Allylation of Ketene Silyl Acetals
Aldehydes and Ketones from Oxidation of Allyl Carbonates . .
á,â-Unsaturated Aldehydes and Ketones from Oxidation of
Allylpalladium Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
á,â-Unsaturated Aldehydes and Ketones from
168
168
169
169
170
171
172
173
173
Oxidation of Enol Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
From Oxidation of Enol Carbonates . . . . . . . . . . . . . . . . . . . . . . . . 175
From Oxidation of Enol Acetates . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
From Oxidation of Silyl Enol Ethers . . . . . . . . . . . . . . . . . . . . . . . . . 176
á,â-Unsaturated Ketones from Decarboxylation of
Allyl â-Oxocarboxylates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
â,ã-Unsaturated Ketones from Reaction of
Allylpalladium Complexes with Acyliron or
Acylnickel Carbanions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
â,ã-Unsaturated Aldehydes and Ketones from
Carbonylation of Allyl Halides with Organostannanes . . . . . . . 179
â,ã-Unsaturated Ketones from Rearrangement of
Cyclic Vinyl Epoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
ã,ä-Unsaturated Ketones from Allylation of
Enolates and Enolate Equivalents . . . . . . . . . . . . . . . . . . . . . . . . . . 181
ã,ä-Unsaturated Ketones from Decarboxylative Allylation of
â-Oxo Esters and Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
Decarboxylative Allylation of Allyl â-Oxocarboxylate Esters . . 184
Decarboxylative Alkylation of â-Oxo Acids with
Allylic Electrophiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
ã,ä-Unsaturated Aldehydes and Ketones from
Rearrangement of Allyl Enol Carbonates . . . . . . . . . . . . . . . . . . . . 187
Allylic Esters from Allylic Acetoxylation of Alkenes . . . . . . . . . . 188
ã-Acetoxy-(E)-á,â-Unsaturated Esters and Sulfones from
Acetoxylation of â,ã-Unsaturated Esters and Sulfones . . . . . . . 188
Allylic Acetoxylation of Simple Alkenes . . . . . . . . . . . . . . . . . . . . . 189
Allylic Esters from Allylpalladium Complexes . . . . . . . . . . . . . . . . 190
Allylic Esters from Reaction of Allyl Electrophiles with
Carboxylate Anions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
Science of Synthesis Original Edition Volume 1
© Georg Thieme Verlag KG
XVI
Table of Contents
1.2.2.36
1.2.2.36.1
Method 36:
Variation 1:
1.2.2.36.2
Variation 2:
1.2.2.36.3
Variation 3:
1.2.2.37
Method 37:
Method 38:
1.2.2.38
1.2.2.40
Method 39:
Method 40:
1.2.2.41
Method 41:
1.2.2.42
Method 42:
1.2.2.43
Method 43:
1.2.2.44
Method 44:
Method 45:
Method 46:
1.2.2.39
1.2.2.45
1.2.2.46
1.2.2.47
1.2.2.48
1.2.2.49
1.2.2.49.1
1.2.2.49.2
1.2.2.49.3
1.2.2.49.4
1.2.2.50
1.2.2.51
Method 47:
Method 48:
Method 49:
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Method 50:
Method 51:
1.2.2.53
Variation 1:
Variation 2:
Method 52:
Method 53:
1.2.2.54
Method 54:
1.2.2.54.1
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Variation 5:
Method 55:
1.2.2.51.1
1.2.2.51.2
1.2.2.52
1.2.2.54.2
1.2.2.54.3
1.2.2.54.4
1.2.2.54.5
1.2.2.55
4-Heterosubstituted 1-Acetoxyalk-2-enes from 1,3-Dienes . . 192
1,4-Diacetoxyalk-2-enes from 1,4-Diacetoxylation
of 1,3-Dienes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
1-Acetoxy-4-chloroalk-2-enes from 1,4-Acetoxychlorination
of 1,3-Dienes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
1-Acetoxy-4-(trifluoroacetoxy)alk-2-enes from
1,4-Acetoxytrifluoroacetoxylation of 1,3-Dienes . . . . . . . . . . . . 195
Allylic Acetates by Rearrangement . . . . . . . . . . . . . . . . . . . . . . . . . 196
Allylic Ethers from Reaction of Allylic Electrophiles with
Alcohols and Alkoxide Anions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
Allylic Alcohols from Oxidation of Allylpalladium Complexes
198
Homoallylic Alcohols by Carbonyl Allylation with
Allyl Organometallics Generated by Umpolung of
Allylpalladium Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
S-Allyl Phosphorothioates from Rearrangement of
O-Allyl Phosphorothioates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
Allylic Sulfones from Reaction of Allylic Electrophiles with
Sulfinates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
Allylic Sulfones from Hydrosulfination of Allenes and
1,3-Dienes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
Allylic Sulfones from Rearrangement of O-Allyl Sulfinates . . . . 206
Allylic Sulfones from 1,3-Rearrangement of Allylic Sulfones . . 207
Unsaturated Sulfones from Protiodepalladation of
[4-Sulfonyl-(1,2,3-ç)-alk-2-enyl]palladium Complexes . . . . . . . 207
Allylic Sulfides from Reaction of Allylic Carbonates with Thiols 208
Allylic Amines from Amination of Allylpalladium Complexes
209
Allylic Amines from Amination of Allylic Electrophiles . . . . . . . 210
Allylic Amination with Primary and Secondary Amines . . . . . . 211
Allylic Amination with Imides and Iminodicarbonates . . . . . . . 213
Allylic Amination with Sulfonamides . . . . . . . . . . . . . . . . . . . . . . . 215
Allylic Amination with Azide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
Allylic Amines from Hydroamination of Allenes . . . . . . . . . . . . . 217
4-Vinyloxazolidin-2-ones from Vinyl Epoxides and
But-2-ene-1,4-diols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
From Vinyl Epoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
From But-2-ene-1,4-diols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220
Homoallylic Amines by Imine Allylation with Allylstannanes
221
Allylic Phosphine Sulfides from Displacement of
Allylic Carboxylates with Diphenylphosphorothioyllithium . . . 222
Allyl Arenes from Coupling of Allylic Electrophiles and
Aryl Organometallics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
From Tetrabutylammonium Difluorotriphenylsilicate . . . . . . . . 223
From Arylstannanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
From Sodium Tetraphenylborate . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
From Arylzincs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
From Aryl Grignard Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
1,3-Dienes from â-Elimination of Allylic Alcohol Derivatives
227
Science of Synthesis Original Edition Volume 1
© Georg Thieme Verlag KG
Table of Contents
1.2.2.56
Method 56:
1.2.2.57
Method 57:
1.2.2.58
Method 58:
1.2.2.59
Method 59:
1.2.2.59.1
Variation 1:
Variation 2:
Method 60:
1.2.2.59.2
1.2.2.60
1.2.2.62
Method 61:
Method 62:
1.2.2.63
Method 63:
1.2.2.64
Method 64:
1.2.2.65
Method 65:
Method 66:
1.2.2.61
1.2.2.66
1.2.3
1.2.3
XVII
1,3-Dienes from Reductive Elimination of Dicarbonates
of Enediols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
1,3-Dienes from Decarboxylative Elimination of
â-Acetoxy Carboxylic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
1,4-Dienes from Coupling of Alkenylzirconiums and
Allylpalladium Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
1,4-Dienes from Coupling of Vinyl Organometallics and
Allyl Electrophiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
From Alkenylaluminum Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . 231
From Vinylstannanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
1,5-Dienes from Coupling of Allylstannanes and
Allyl Electrophiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
1,6-Dienes from Dimerization of Butadienes (Telomerization) 235
Methylenecyclopentenes via [3+2]-Cycloaddition Reactions
of Trimethylenemethanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
Vinylcyclopentanes via [3+2]-Cycloaddition Reactions of
Vinylcyclopropanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
Vinylcyclopentanes from Palladium-Catalyzed
Intramolecular Ene Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
Alkenes from Reduction of Allylic Heterosubstituents . . . . . . . 243
4-Substituted Alkenes from Alkylation of Stabilized
Carbon Nucleophiles with Allyl Electrophiles . . . . . . . . . . . . . . . . 245
Product Subclass 3: Palladium±Alkyne Complexes
J. M. Takacs, S. Vayalakkada, and X. Jiang
Product Subclass 3: Palladium±Alkyne Complexes . . . . . . . . . . . . . . . . . . . . . . . 265
Synthesis of Product Subclass 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
1.2.3.1
Method 1:
Preparation and Characterization of
Palladium±Alkyne Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
Applications of Product Subclass 3 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 268
1.2.3.2.1
Method 2:
Variation 1:
1.2.3.2.2
Variation 2:
1.2.3.2.3
Variation 3:
1.2.3.3
1.2.3.3.1
Method 3:
Variation 1:
1.2.3.3.2
Variation 2:
1.2.3.3.3
Variation 3:
1.2.3.2
Addition of Oxygen Nucleophiles: Carboxylates . . . . . . . . . . . . . 268
Intramolecular Addition of Carboxylates Followed by
Protonation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
Intramolecular Addition of Carboxylates Followed by
Allylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
Intramolecular Addition of Carboxylates
Followed by Arylation or Vinylation . . . . . . . . . . . . . . . . . . . . . . . . 274
Addition of Oxygen Nucleophiles: Hydroxy Moieties . . . . . . . . 276
Intramolecular Addition of Alcohols Followed by
Protonation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
Intramolecular Addition of Alcohols Followed by
Carbon Monoxide Insertion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
Intramolecular Addition of Alcohols Followed by Allylation . . 282
Science of Synthesis Original Edition Volume 1
© Georg Thieme Verlag KG
XVIII
Table of Contents
1.2.3.3.4
Variation 4:
1.2.3.4
1.2.3.4.1
Method 4:
Variation 1:
1.2.3.4.2
Variation 2:
1.2.3.4.3
Variation 3:
1.2.3.4.4
Variation 4:
1.2.3.5
1.2.3.5.1
Method 5:
Variation 1:
1.2.3.5.2
Variation 2:
1.2.3.5.3
Variation 3:
1.2.3.6
1.2.3.6.2
Method 6:
Variation 1:
Variation 2:
1.2.3.6.3
Variation 3:
1.2.3.6.4
Variation 4:
Variation 5:
1.2.3.6.1
1.2.3.6.5
Intramolecular Addition of Alcohols Followed by
Vinylation or Arylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Addition of Nitrogen Nucleophiles . . . . . . . . . . . . . . . . . . . . . . . . .
Intramolecular Addition of Nitrogen Nucleophiles
Followed by Protonation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Intramolecular Addition of Nitrogen Nucleophiles
Followed by Allylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Method 7:
Variation 1:
1.2.3.7.2
Variation 2:
1.2.3.7.3
Variation 3:
1.2.4
Product Subclass 4: Palladium±Alkene Complexes
J. M. Takacs and S. Vayalakkada
1.2.4
288
291
Intramolecular Addition of Nitrogen Nucleophiles
Followed by Vinylation or Arylation . . . . . . . . . . . . . . . . . . . . . . . . 294
Intramolecular Addition of Nitrogen Nucleophiles
Followed by Vinyl or Aryl Carbonylation . . . . . . . . . . . . . . . . . . . . 297
Addition of Carbon Nucleophiles . . . . . . . . . . . . . . . . . . . . . . . . . . . 298
Intramolecular Addition of Malononitriles to Alkynes
under Neutral Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 299
Tandem Michael Addition Followed by Intramolecular
Addition of Malonate Derivatives to Alkynes . . . . . . . . . . . . . . . . 301
Intramolecular Addition of Malonate Derivatives to Alkynes
under Strongly Basic Conditions: Four Modes of Reaction . . . 302
Addition of Sulfur Nucleophiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
Addition of Arenethiols to Alkynes To Form Vinyl Sulfides . . . 304
Thiocarbonylation of Alkynes with Thiols and
Carbon Monoxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 306
Addition of Diaryl Disulfides to Alkynes To Form
1,2-Disulfanylalkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308
Thiocarbonylation of Acetylenes with Disulfides . . . . . . . . . . . . 309
Palladium-Catalyzed Thioboration of Acetylenes
with 9-(Alkylsulfanyl)-9-borabicyclo[3.3.1]nonanes . . . . . . . . . . 311
Addition of Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312
Palladium-Catalyzed Addition of Halides to Alkynes
Followed by Alkene Insertion and Protonolysis . . . . . . . . . . . . . . 313
Palladium-Catalyzed Addition of Halides to Alkynes
Followed by Alkene Insertion and â-Elimination . . . . . . . . . . . . . 314
Palladium-Catalyzed Addition of Halides to Alkynes
Followed by Alkene Insertion and Oxidation . . . . . . . . . . . . . . . . 315
1.2.3.7.1
1.2.3.7
284
287
Product Subclass 4: Palladium±Alkene Complexes . . . . . . . . . . . . . . . . . . . . . . . 319
Synthesis of Product Subclass 4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 320
1.2.4.1
1.2.4.2
Method 1:
Method 2:
From a Palladium(II) Salt and an Alkene . . . . . . . . . . . . . . . . . . . . 320
From Palladium(0) and an Alkene . . . . . . . . . . . . . . . . . . . . . . . . . . 321
Applications of Product Subclass 4 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 322
1.2.4.3
Method 3:
Palladium-Catalyzed Intermolecular Addition
of Oxygen Nucleophiles: Water and Alcohols . . . . . . . . . . . . . . . 322
Science of Synthesis Original Edition Volume 1
© Georg Thieme Verlag KG
Table of Contents
1.2.4.3.1
Variation 1:
1.2.4.3.2
1.2.4.3.5
Variation 2:
Variation 3:
Variation 4:
Variation 5:
1.2.4.3.6
Variation 6:
1.2.4.3.7
Variation 7:
1.2.4.3.8
Variation 8:
1.2.4.3.9
1.2.4.3.10
Variation 9:
Variation 10:
1.2.4.4
Method 4:
1.2.4.4.1
Variation 1:
1.2.4.4.2
Variation 2:
1.2.4.4.3
Variation 3:
1.2.4.4.4
Variation 4:
Variation 5:
1.2.4.3.3
1.2.4.3.4
1.2.4.4.5
1.2.4.4.7
Variation 6:
Variation 7:
1.2.4.4.8
Variation 8:
1.2.4.5
Method 5:
Variation 1:
1.2.4.4.6
1.2.4.5.1
1.2.4.6
Variation 2:
Method 6:
1.2.4.6.1
Variation 1:
1.2.4.6.2
Variation 2:
1.2.4.6.3
Variation 3:
1.2.4.6.4
Variation 4:
1.2.4.5.2
Addition of Water to Terminal Alkenes To Form Ketones;
the Wacker Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
The Wacker Oxidation Using a Fluorous Biphasic System . . . .
The Wacker Oxidation in Solid-Phase Synthesis . . . . . . . . . . . . .
Addition of Water to Terminal Alkenes To Form Aldehydes . .
XIX
323
327
329
330
Addition of Water to Allylic Carbonates
To Form á,â-Unsaturated Aldehydes . . . . . . . . . . . . . . . . . . . . . . . 333
Palladium-Catalyzed Oxidative Removal of
Allyl Protecting Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 334
Palladium-Catalyzed Oxidation of Internal Alkenes:
Allylic and Homoallylic Ethers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335
Palladium-Catalyzed Oxidation of Internal Alkenes:
Unsaturated Carbonyl Compounds . . . . . . . . . . . . . . . . . . . . . . . . . 337
Intermolecular Addition of Alcohol To Form Acetals and Ketals 338
Intermolecular Addition of Alcohol To Form Acetals
from á,â-Unsaturated Carbonyl Compounds . . . . . . . . . . . . . . . 339
Palladium-Catalyzed Heterocyclization:
Intramolecular Addition of Oxygen Nucleophiles . . . . . . . . . . . . 340
Intramolecular Addition of Alcohol Followed by
â-Hydroxide Elimination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 340
Intramolecular Addition of Alcohol Followed by
â-Hydrogen Elimination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 342
Intramolecular Addition of Alcohol Followed by
â-Hydrogen Elimination: A Catalytic Asymmetric Variant . . . . 344
Double Addition of Alcohol To Form Mixed Ketals . . . . . . . . . . . 345
Intramolecular Addition of Alcohol Followed by
Carbon Monoxide Insertion and Alcoholysis . . . . . . . . . . . . . . . . 347
Addition of Alcohol Followed by Alkene Insertion . . . . . . . . . . . 350
Intramolecular Addition of Carboxylate Followed by
â-Hydride Elimination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352
Intramolecular Addition of Carboxylate Followed by
Carbon Monoxide Trapping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
Intermolecular Addition of Nitrogen Nucleophiles . . . . . . . . . . 355
Intermolecular Addition of Amines Followed by
â-Hydride Elimination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
Intermolecular Addition of Amides and Carbamates . . . . . . . . 356
Palladium-Catalyzed Heterocyclization:
Intramolecular Addition of Nitrogen Nucleophiles . . . . . . . . . . . 357
Intramolecular Addition of Amine Followed by
â-Hydride Elimination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
Intramolecular Addition of Amine Followed by â-Elimination:
In Situ Reduction of Aromatic Nitro Compounds . . . . . . . . . . . . 359
Intramolecular Addition of Amine Followed by
Carbon Monoxide Insertion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 360
Intramolecular Addition of N-Sulfonyl and N-Acyl Derivatives
Followed by â-Hydrogen Elimination . . . . . . . . . . . . . . . . . . . . . . . 361
Science of Synthesis Original Edition Volume 1
© Georg Thieme Verlag KG
XX
Table of Contents
1.2.4.6.5
Variation 5:
1.2.4.6.6
Variation 6:
1.2.4.7
Method 7:
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Variation 5:
Variation 6:
1.2.4.7.1
1.2.4.7.2
1.2.4.7.3
1.2.4.7.4
1.2.4.7.5
1.2.4.7.6
1.3
Intramolecular Addition of N-Acyl and N-Sulfonyl Derivatives
Followed by Carbon Monoxide Insertion (Carbonylation) . . . .
Intramolecular Addition of N-Acyl and N-Sulfonyl Derivatives
Followed by Alkene Insertion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Palladium(II)-Catalyzed [3,3]-Sigmatropic Rearrangements . .
Palladium(II)-Catalyzed Cope Rearrangements . . . . . . . . . . . . . .
Oxy-Cope Rearrangement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Claisen and Thia-Claisen Rearrangements . . . . . . . . . . . . . . . . . .
Enolate Claisen Rearrangements . . . . . . . . . . . . . . . . . . . . . . . . . . .
Allylic Imidate Rearrangements . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Allylic Ester Rearrangement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
363
367
367
368
371
371
374
375
379
Product Class 3: Organometallic Complexes of Platinum
A. Ogawa and T. Hirao
1.3
Product Class 3: Organometallic Complexes of Platinum . . . . . . . . . . . . . . . . . 389
1.3.1
Product Subclass 1: Platinum±Cyclopentadienyl Complexes . . . . . . . . . . . . . 389
Synthesis of Product Subclass 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
1.3.1.1
Method 1:
Cyclopentadienylplatinum(II) Complexes from
Platinum Halide Complexes and Cyclopentadienyl Anions . . . 389
Cyclopentadienylplatinum(IV) Complexes from
Platinum Halide Complexes and Cyclopentadienyl Anions . . . 391
1.3.1.2
Method 2:
1.3.2
Product Subclass 2: Platinum±Diene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . 394
Synthesis of Product Subclass 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394
1.3.2.1
1.3.2.2
1.3.2.3
1.3.2.4
1.3.2.5
1.3.2.6
Method 1:
Method 2:
Method 3:
Method 4:
Method 5:
Method 6:
Platinum(0)±Allene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Platinum(II)±Allene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Platinum(0)±Conjugated Polyene Complexes . . . . . . . . . . . . . . .
Platinum(II)±Conjugated Polyene Complexes . . . . . . . . . . . . . . .
Platinum(0)±Nonconjugated Polyene Complexes . . . . . . . . . . .
Platinum(II)±Nonconjugated Polyene Complexes . . . . . . . . . . .
394
396
397
399
400
402
Applications of Product Subclass 2 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 404
1.3.2.7
Method 7:
Platinum(0)-Catalyzed Dimerization of Conjugated Dienes
and Related Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
1.3.3
Product Subclass 3: Platinum±Allyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
Synthesis of Product Subclass 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
1.3.3.1
Method 1:
1.3.3.2
Method 2:
1.3.3.3
Method 3:
1.3.3.4
Method 4:
Allylplatinum Complexes from Platinum(II) Complexes
and Allylic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
Allylplatinum Complexes by Addition of
Platinum(II) Hydrides to Unsaturated Bonds . . . . . . . . . . . . . . . . 406
Allylplatinum Complexes from
Allylic Platinum(II) Precursors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 407
Allylplatinum Complexes from Platinum(0) Precursors . . . . . . 409
Science of Synthesis Original Edition Volume 1
© Georg Thieme Verlag KG
1.3.4
Table of Contents
XXI
Product Subclass 4: Platinum±Alkyne Complexes . . . . . . . . . . . . . . . . . . . . . . . .
411
Synthesis of Product Subclass 4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
411
1.3.4.1
Method 1:
1.3.4.2
Method 2:
1.3.4.3
Method 3:
1.3.4.4
Method 4:
Platinum(0)±Alkyne Complexes Starting from
Platinum(II) Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 411
Platinum(0)±Alkyne Complexes by Ligand-Exchange Reactions
with Platinum(0)±Phosphine Complexes . . . . . . . . . . . . . . . . . . . 413
Platinum(0)±Alkyne Complexes by Ligand-Exchange Reactions
with Platinum(0)±Alkene Complexes . . . . . . . . . . . . . . . . . . . . . . . 414
Platinum(II)±Alkyne Complexes by Ligand-Exchange Reactions
with Platinum(II) Halide and Related Complexes . . . . . . . . . . . . 416
Applications of Product Subclass 4 in Organic Synthesis . . . . . . . . . . . . . . . . . . . .
1.3.4.5
Method 5:
1.3.4.5.1
Variation 1:
Variation 2:
1.3.4.5.2
1.3.5
Catalytic Addition of Main Group Element±Hydrogen Bond
Compounds to Acetylenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Hydrosilylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Addition of Other Main Group
Element±Hydrogen Bond Compounds . . . . . . . . . . . . . . . . . . . . .
417
417
417
418
Product Subclass 5: Platinum±Alkene Complexes . . . . . . . . . . . . . . . . . . . . . . . . 420
Synthesis of Product Subclass 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 420
1.3.5.3
Method 1:
Method 2:
Method 3:
1.3.5.4
Method 4:
1.3.5.1
1.3.5.2
1.3.5.5
Method 5:
1.3.5.6
Method 6:
Platinum(0)±Monoalkene Polydentate Complexes . . . . . . . . . .
Platinum(II)±Monoalkene Polydentate Complexes . . . . . . . . . .
Platinum(0)±Monoalkene Monodentate Complexes
Starting from Platinum(II) Complexes . . . . . . . . . . . . . . . . . . . . . .
Platinum(0)±Monoalkene Monodentate Complexes
by Ligand-Exchange Reactions with Platinum(0) Complexes .
420
421
423
425
Platinum(II)±Monoalkene Monodentate Complexes
by Ligand-Exchange Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 427
Pentacoordinate Platinum(II)±Monoalkene
Monodentate Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 428
Applications of Product Subclass 5 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 430
1.3.5.7
1.3.5.8
Method 7:
Method 8:
Catalytic Hydrogenation of Alkenes . . . . . . . . . . . . . . . . . . . . . . . . 430
Catalytic Hydrosilylation of Alkenes and
Related Addition Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 431
Product Class 4: Organometallic Complexes of Cobalt
M. Malacria, C. Aubert, and J.-L. Renaud
1.4
1.4
Product Class 4: Organometallic Complexes of Cobalt . . . . . . . . . . . . . . . . . . . 439
1.4.1
Product Subclass 1: Cobalt±Dienyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . 439
Synthesis of Product Subclass 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 440
1.4.1.1
Method 1:
1.4.1.1.1
Variation 1:
Variation 2:
1.4.1.1.2
Bis(alkene)(cyclopentadienyl)cobalt(I) Complexes by
Ligand Exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 440
Via Displacement of Carbon Monoxide . . . . . . . . . . . . . . . . . . . . . 440
Via Ligand Substitution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 441
Science of Synthesis Original Edition Volume 1
© Georg Thieme Verlag KG
XXII
Table of Contents
1.4.1.2
Method 2:
1.4.1.2.1
1.4.1.2.2
Variation 1:
Variation 2:
1.4.1.3
Method 3:
1.4.1.4
Method 4:
1.4.1.5
Method 5:
Bis(alkene)(ç5-cyclopentadienyl)cobalt(I) Complexes
by Reduction of Cobalt(II) Complexes . . . . . . . . . . . . . . . . . . . . . . 442
Via Elimination of Alkali Metal Cyclopentadienide . . . . . . . . . . . 442
Via Reduction of (Pentaalkylcyclopentadienyl)cobalt(II)
Halide Dimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 443
Dicarbonyl(ç5-cyclopentadienyl)cobalt(I) by
Oxidative Addition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 444
Cyclopentadienyl(maleoyl)cobalt(III) and
Cyclopentadienyl(phthaloyl)cobalt(III) Complexes by
Insertion into Substituted Cyclobutenediones . . . . . . . . . . . . . . 444
Cyclopentadienylbis(triarylphosphine)cobalt(I) Complexes
by Reduction of Cobalt(III) Complexes . . . . . . . . . . . . . . . . . . . . . . 445
Applications of Product Subclass 1 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 446
Hydroacylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 446
Epoxide Opening . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 447
Inter- and Intramolecular [2 + 2 + 2] Cyclizations . . . . . . . . . . . . . 448
Intermolecular [2 + 2 + 2] Cyclization of Diynes and Nitriles:
Synthesis of Pyridines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 448
Inter- and Intramolecular [2 + 2 + 2] Cyclization of Triynes
in Aromatic and Aqueous Solvents . . . . . . . . . . . . . . . . . . . . . . . . . 451
Inter- and Intramolecular [2 + 2 + 2] Cyclization of
Enediynes and Allenediynes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 455
Inter- and Intramolecular [2 + 2 + 2] Cyclization of
Diynes with Heteroatom-Substituted Multiple Bonds . . . . . . . . 458
Inter- and Intramolecular [2 + 2] Cyclizations . . . . . . . . . . . . . . . . 461
Cobalt-Mediated Ene±Yne Cyclizations . . . . . . . . . . . . . . . . . . . . . 462
Alder Ene-Type Cyclizations of Enynes and Allenynes . . . . . . . . 463
Ene-Type Reactions of â-Oxo Ester e-Ynes . . . . . . . . . . . . . . . . . . 464
Synthesis of Quinones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 466
1.4.1.8.1
Method 6:
Method 7:
Method 8:
Variation 1:
1.4.1.8.2
Variation 2:
1.4.1.8.3
Variation 3:
1.4.1.8.4
Variation 4:
1.4.1.9
1.4.1.11
Method 9:
Method 10:
Variation 1:
Variation 2:
Method 11:
1.4.2
Product Subclass 2: Cobalt±Diene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 467
1.4.1.6
1.4.1.7
1.4.1.8
1.4.1.10
1.4.1.10.1
1.4.1.10.2
Synthesis of Product Subclass 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 468
1.4.2.1
Method 1:
Tricarbonyl(ç4-diene)cobalt(I) Tetrafluoroborate Complexes
468
Applications of Product Subclass 2 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 468
1,4-Difunctionalization of Dienes . . . . . . . . . . . . . . . . . . . . . . . . . . 468
Synthesis of Z-Disubstituted Alkenes . . . . . . . . . . . . . . . . . . . . . . . 469
Synthesis of Heterocyclic Compounds . . . . . . . . . . . . . . . . . . . . . . 469
1.4.2.2.2
Method 2:
Variation 1:
Variation 2:
1.4.3
Product Subclass 3: Cobalt±Allyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 472
1.4.2.2
1.4.2.2.1
Synthesis of Product Subclass 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 472
1.4.3.1
1.4.3.2
1.4.3.3
1.4.3.4
Method 1:
Method 2:
Method 3:
Method 4:
Allylcobalt Complexes by Ligand Exchange . . . . . . . . . . . . . . . . .
Allylcobalt Complexes by Elimination of Leaving Groups . . . . .
Allylcobalt Complexes by Hydridocobaltation of 1,3-Dienes
Allylcobalt Complexes by Addition of Alkyl- and
Acylcobalt Complexes to Conjugated Dienes and
Various Unsaturated Compounds . . . . . . . . . . . . . . . . . . . . . . . . . .
Science of Synthesis Original Edition Volume 1
© Georg Thieme Verlag KG
472
473
475
476
Table of Contents
XXIII
Applications of Product Subclass 3 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 478
1.4.3.5
1.4.3.6
Method 5:
Method 6:
Synthesis of Acyldienes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1,4-Acylation/Alkylation of 1,3-Dienes and Allenes:
Synthesis of Substituted Enones . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acylation±Cyclization of Allenes: Synthesis of Heterocycles . .
Synthesis of Butenolides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
478
479
481
482
1.4.3.8
Method 7:
Method 8:
1.4.4
Product Subclass 4: Miscellaneous Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . 483
1.4.3.7
Synthesis of Product Subclass 4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 483
1.4.4.1
1.4.4.1.1
1.4.4.1.2
1.4.4.1.3
1.4.4.2
1.4.4.3
1.4.4.4
1.4.4.5
1.4.4.6
1.4.4.7
Method 1:
Variation 1:
Variation 2:
Variation 3:
Method 2:
Method 3:
Method 4:
Method 5:
Method 6:
Method 7:
Cobalt(III) Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From Cobalt(III) Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From Cobalt(II) Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From Cobalt(I) Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
483
484
485
486
(ì-Alkyne)hexacarbonyldicobalt(0) Complexes by
Ligand Exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 487
Chlorotris(triphenylphosphine)cobalt(I) . . . . . . . . . . . . . . . . . . . . 488
Tetrakis(trimethylphosphine)cobalt(0) by Reduction
of Cobalt(II) Chloride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 489
Tetracarbonylhydridocobalt(I) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 490
Tris(acetylacetonato)cobalt(III) as a Precatalyst . . . . . . . . . . . . . 491
Cobalt(II) Complexes as Precatalysts . . . . . . . . . . . . . . . . . . . . . . . 491
Applications of Product Subclass 4 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 493
1.4.4.11.1
Method 8:
Method 9:
Method 10:
Method 11:
Variation 1:
1.4.4.11.2
Variation 2:
1.4.4.8
1.4.4.9
1.4.4.10
1.4.4.11
1.4.4.12
1.4.4.12.1
1.4.4.12.2
1.4.4.13
1.4.4.13.1
1.4.4.13.2
1.4.4.14
1.4.4.14.1
1.4.4.14.2
1.4.4.14.3
1.4.4.15
1.4.4.15.1
1.4.4.15.2
Method 12:
Variation 1:
Variation 2:
Method 13:
Variation 1:
Variation 2:
Method 14:
Variation 1:
Variation 2:
Variation 3:
Method 15:
Variation 1:
Variation 2:
Reformatsky- and Aldol-Type Reactions . . . . . . . . . . . . . . . . . . . .
Silylcarbonylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Hydroformylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Synthesis of Epoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Synthesis of Enantiomerically Pure Epoxides Using
Cobalt(III) Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Synthesis of Epoxides Using Cobalt(II) Complexes under
Neutral Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Carbon-Heteroatom Bond Formation . . . . . . . . . . . . . . . . . . . . . .
Cobalt(II)-Mediated Aerobic Oxygenation of Alkenes . . . . . . . .
Cobalt(II) Chloride Catalyzed Carbon-Heteroatom
Bond Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Synthesis of Carbonyl Compounds . . . . . . . . . . . . . . . . . . . . . . . . .
Syntheses Catalyzed by Cobalt(II) Complexes . . . . . . . . . . . . . . .
Syntheses Catalyzed by
Chlorotris(triphenylphosphine)cobalt(I) . . . . . . . . . . . . . . . . . . . .
C-C Bond Formation by Addition . . . . . . . . . . . . . . . . . . . . . . . . . .
Formation of C-C Bonds via Radical Addition Reactions . . . . .
The Nicholas Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
The Inter- and Intramolecular Pauson±Khand Reaction . . . . . .
C-C Bond Formation by Rearrangement . . . . . . . . . . . . . . . . . . .
Rearrangement of 1-(Alk-1-ynyl)cyclopropanols . . . . . . . . . . . .
493
494
496
498
498
499
500
500
501
502
502
504
504
505
508
512
517
518
Diels±Alder Reaction with 2-Cobaloxime-Substituted
1,3-Dienes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 519
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© Georg Thieme Verlag KG
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Table of Contents
1.4.4.15.3
Variation 3:
Variation 4:
1.4.4.15.4
1.5
Homo-Diels±Alder Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 520
Additional Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521
Product Class 5: Organometallic Complexes of Rhodium
I. Ojima, A. T. Vu, and D. Bonafoux
1.5
Product Class 5: Organometallic Complexes of Rhodium . . . . . . . . . . . . . . . . . 531
1.5.1
Product Subclass 1: Rhodium±Arene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . 532
Synthesis of Product Subclass 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 532
Cationic Complexes by Ligand Substitution . . . . . . . . . . . . . . . . .
From Arenes and Cationic Rhodium±Diene Complexes . . . . . .
From Arenes and Rhodium±Acetylacetonate Complexes . . . .
From Arenes and Rhodium(III) Chloride . . . . . . . . . . . . . . . . . . . . .
From Arenes and Rhodium±Acetate Complexes . . . . . . . . . . . .
Via Displacement of Weakly Bound Ligands . . . . . . . . . . . . . . . . .
1.5.1.1.5
Method 1:
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Variation 5:
1.5.2
Product Subclass 2: Rhodium±Cumulene Complexes . . . . . . . . . . . . . . . . . . . . . 536
1.5.1.1
1.5.1.1.1
1.5.1.1.2
1.5.1.1.3
1.5.1.1.4
532
532
533
534
534
535
Synthesis of Product Subclass 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 536
Cumulatriene Complexes by Ligand Substitution . . . . . . . . . . . . 536
Cumulapentaene Complex by Ligand Substitution . . . . . . . . . . 537
1.5.2.2
Method 1:
Method 2:
1.5.3
Product Subclass 3: Rhodium±Dienyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . 537
1.5.2.1
Synthesis of Product Subclass 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 538
1.5.3.1.2
Method 1:
Variation 1:
Variation 2:
1.5.3.2
Method 2:
1.5.3.1
1.5.3.1.1
Cyclopentadienylrhodium Complexes by Ligand Substitution
From Cyclopentadienyl Anions and Rhodium Halides . . . . . . . .
Cationic Bis(cyclopentadienyl) Complexes by
Ligand Substitution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From Pentamethylcyclopentadienyl Anions and
Rhodium Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Dimeric Pentamethylcyclopentadienyl Complexes . . . . . . . . . .
Monomeric Pentamethylcyclopentadienyl Complexes . . . . . . .
Indenyl Complexes by Ligand Substitution . . . . . . . . . . . . . . . . . .
Acyclic Pentadienyl Complexes by Dehydration . . . . . . . . . . . . .
ç5-Cyclohexadienyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Via Ligand Substitution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Cationic Complexes via Hydride Abstraction . . . . . . . . . . . . . . . .
Via Nucleophilic Addition to an Arene Ligand . . . . . . . . . . . . . . .
Norbornadienyl Complexes by Dehydration . . . . . . . . . . . . . . . . .
ç5-Cycloheptadienyl Complexes by Nucleophilic Addition . . .
ç5-Cyclooctadienyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
538
538
539
540
541
542
542
544
544
545
546
546
547
548
548
1.5.3.8
Variation 1:
Variation 2:
Method 3:
Method 4:
Method 5:
Variation 1:
Variation 2:
Variation 3:
Method 6:
Method 7:
Method 8:
1.5.4
Product Subclass 4: Rhodium±Diene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . 549
1.5.3.2.1
1.5.3.2.2
1.5.3.3
1.5.3.4
1.5.3.5
1.5.3.5.1
1.5.3.5.2
1.5.3.5.3
1.5.3.6
1.5.3.7
Synthesis of Product Subclass 4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 549
1.5.4.1
1.5.4.2
1.5.4.2.1
Method 1:
Method 2:
Variation 1:
Allene Complexes by Ligand Substitution . . . . . . . . . . . . . . . . . . . 549
Alka-1,3-diene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 550
Via Ligand Substitution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 551
Science of Synthesis Original Edition Volume 1
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Table of Contents
1.5.4.2.2
1.5.4.2.3
1.5.4.2.4
1.5.4.2.5
1.5.4.2.6
1.5.4.3
1.5.4.3.1
1.5.4.3.2
1.5.4.3.3
1.5.4.3.4
1.5.4.4
1.5.4.4.1
1.5.4.4.2
1.5.4.4.3
1.5.4.4.4
1.5.4.5
1.5.4.6
Variation 2:
Variation 3:
Variation 4:
Variation 5:
Variation 6:
Method 3:
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Method 4:
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Method 5:
Method 6:
XXV
Via Displacement of Weakly Bound Ligands . . . . . . . . . . . . . . . . .
Cationic Complexes via Ligand Substitution . . . . . . . . . . . . . . . .
Cyclobutadiene Complexes via Alkyne Cyclodimerization . . . .
ç4-Cyclopentadiene Complexes via Nucleophilic Addition
to ç5-Cyclopentadienyl Ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . .
ç4-Cyclopentadienone Complexes . . . . . . . . . . . . . . . . . . . . . . . . .
Cycloocta-1,5-diene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Via Ligand Substitution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Via Displacement of Weakly Bound Ligands . . . . . . . . . . . . . . . . .
555
556
558
558
559
Homoleptic Cationic Cycloocta-1,5-diene Complexes
via Anionic Ligand Abstraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Monomeric Cycloocta-1,5-diene Complexes . . . . . . . . . . . . . . . .
Norbornadiene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Via Ligand Substitution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Via Displacement of Weakly Bound Ligands . . . . . . . . . . . . . . . . .
560
561
563
563
564
Homoleptic, Cationic Norbornadiene Complexes
via Anionic Ligand Abstraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Monomeric Norbornadiene Complexes . . . . . . . . . . . . . . . . . . . . .
Cycloocta-1,3,5,7-tetraene Complexes . . . . . . . . . . . . . . . . . . . . .
Synthesis of Cationic Chiral Diene Complexes . . . . . . . . . . . . . . .
565
566
567
569
551
553
553
Applications of Product Subclass 4 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 571
Reactions Involving Allenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Carbonylative [4 + 1] Cycloaddition of Vinylallene . . . . . . . . . . .
[4 + 2] Diene±Allene Cycloaddition . . . . . . . . . . . . . . . . . . . . . . . . .
[5 + 2] Vinylcyclopropane±Allene Cycloaddition . . . . . . . . . . . . .
[4 + 2] Cycloaddition Involving 1,3-Dienes . . . . . . . . . . . . . . . . . .
1.5.4.8
Method 7:
Variation 1:
Variation 2:
Variation 3:
Method 8:
1.5.5
Product Subclass 5: Rhodium±Allyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . 577
1.5.4.7
1.5.4.7.1
1.5.4.7.2
1.5.4.7.3
571
571
573
573
574
Synthesis of Product Subclass 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 577
1.5.5.1
1.5.5.2
1.5.5.3
1.5.5.4
1.5.5.5
1.5.5.6
Method 1:
Method 2:
Method 3:
Method 4:
Method 5:
Method 6:
Monoallyl Complexes via Transmetalation . . . . . . . . . . . . . . . . . .
Allyl Complexes by Hydrometalation . . . . . . . . . . . . . . . . . . . . . . .
Allyl Complexes by Allylation of Metal Salts . . . . . . . . . . . . . . . . .
Allyl Complexes by Oxidative Addition . . . . . . . . . . . . . . . . . . . . .
Bis(allyl) Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Tris(allyl) Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
577
579
583
583
585
587
Applications of Product Subclass 5 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 588
Metallo-Ene Cyclization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 588
1.5.5.7
Method 6:
1.5.6
Product Subclass 6: Rhodium±Alkyne Complexes . . . . . . . . . . . . . . . . . . . . . . . . 589
Synthesis of Product Subclass 6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589
1.5.6.1
1.5.6.2
1.5.6.3
Method 1:
Method 2:
Method 3:
Via Simple Alkyne Addition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589
Via Displacement of Weakly Bound Ligands . . . . . . . . . . . . . . . . . 590
Alkyne-Bridged Dimeric Complexes via Ligand Displacement 592
Applications of Product Subclass 6 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 594
1.5.6.4
Method 4:
[2 + 2 + 2] Cycloaddition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 594
Science of Synthesis Original Edition Volume 1
© Georg Thieme Verlag KG
XXVI
Table of Contents
1.5.6.4.1
1.5.6.8.2
Variation 1:
Variation 2:
Method 5:
Method 6:
Variation 1:
Variation 2:
Method 7:
Method 8:
Variation 1:
Variation 2:
1.5.7
Product Subclass 7: Rhodium±Alkene Complexes . . . . . . . . . . . . . . . . . . . . . . . . 603
1.5.6.4.2
1.5.6.5
1.5.6.6
1.5.6.6.1
1.5.6.6.2
1.5.6.7
1.5.6.8
1.5.6.8.1
[2 + 2 + 2] Cyclotrimerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Silylcarbotricyclization of Triynes . . . . . . . . . . . . . . . . . . . . . . . . . . .
Rhodium-Catalyzed Pauson±Khand Reaction . . . . . . . . . . . . . . .
[5 + 2] Vinylcyclopropane±Alkyne Cycloaddition . . . . . . . . . . . .
Intramolecular [5 + 2] Cycloaddition . . . . . . . . . . . . . . . . . . . . . . . .
Intermolecular [5 + 2] Cycloaddition . . . . . . . . . . . . . . . . . . . . . . . .
Enyne Carbocyclization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Silylcarbocyclization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Silylcarbobicyclization of 1,6-Diynes . . . . . . . . . . . . . . . . . . . . . . . .
Silylcarbocyclization of Enynes . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
594
596
596
597
598
599
600
600
600
601
Synthesis of Product Subclass 7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 604
1.5.7.1
1.5.7.2
1.5.7.3
1.5.7.4
Method 1:
Method 2:
Method 3:
Method 4:
Via Ligand Substitution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Monomeric Complexes via
Chlorine-Bridge Cleavage Reactions . . . . . . . . . . . . . . . . . . . . . . . .
Via Displacement of the Ethene Ligand . . . . . . . . . . . . . . . . . . . . .
Via Displacement of Weakly Bound Ligands . . . . . . . . . . . . . . . . .
604
605
606
607
Applications of Product Subclass 7 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 608
1.5.7.5
1.5.7.6
1.5.7.7
1.6
Method 5:
Method 6:
Method 7:
[5 + 2] Vinylcyclopropane±Alkene Cycloaddition . . . . . . . . . . . . 608
Carbocyclization of 1,6-Dienes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 609
Intramolecular Hydroacylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 610
Product Class 6: Organometallic Complexes of Iridium
J. M. OConnor
1.6
Product Class 6: Organometallic Complexes of Iridium . . . . . . . . . . . . . . . . . . . 617
1.6.1
Product Subclass 1: Iridium±Arene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . 617
Synthesis of Product Subclass 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 618
1.6.1.1
Method 1:
1.6.1.2
Method 2:
1.6.1.2.1
Variation 1:
1.6.1.2.2
Variation 2:
1.6.1.2.3
1.6.1.3
Variation 3:
Variation 4:
Variation 5:
Variation 6:
Method 3:
1.6.1.4
Method 4:
1.6.1.2.4
1.6.1.2.5
1.6.1.2.6
Preparation of Cationic Iridium(I)±Arene Complexes by
Ligand Substitution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 618
Preparation of Cationic Iridium(I)±Arene Complexes by
Elimination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 618
From [Ir2(ì-Cl)2(ç4-cod)2] or [Ir2(ì-Cl)2(ç4-Me3TFB)2] and
Silver(I) Tetrafluoroborate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 618
From [Ir(acac)(ç4-cod)] and
Triphenylcarbenium Tetrafluoroborate . . . . . . . . . . . . . . . . . . . . . 620
From [Ir2(ì-OMe)2(ç4-cod)2] and Tetrafluoroboric Acid . . . . . . 620
From [IrCl(ç4-TFB)2] and Silver(I) Tetrafluoroborate . . . . . . . . . . 621
From [Ir2(ì-Cl)2Cl2H2(ç4-cod)2] and Silver(I) Tetrafluoroborate 622
From [IrH2(OCMe2)2(PPh3)2]SbF6 . . . . . . . . . . . . . . . . . . . . . . . . . . . 623
Preparation of Cationic Iridium(I)±Arene Complexes by
Addition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 623
Preparation of Dicationic Iridium(III)±Arene Complexes by
Elimination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 624
Science of Synthesis Original Edition Volume 1
© Georg Thieme Verlag KG
Table of Contents
1.6.1.4.1
Variation 1:
1.6.1.4.2
Variation 2:
1.6.1.4.3
Variation 3:
XXVII
From [Ir2(Cp*)2(ì-Cl)2Cl2] and Silver(I) Hexafluorophosphate
or Tetrafluoroborate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 624
From [Ir2(Cp*)2(ì-Cl)2Cl2] and Silver(I) Tetrafluoroborate
Using an Acidic Workup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 626
From [Ir2(Cp*)2(ì-Cl)2Cl2] and Trifluoroacetic Acid . . . . . . . . . . . 627
Applications of Product Subclass 1 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 628
Dehydration of Cyclohexene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 628
1.6.1.5
Method 5:
1.6.2
Product Subclass 2: Iridium±Dienyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . 628
Synthesis of Product Subclass 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 630
1.6.2.1
Method 1:
1.6.2.1.1
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Variation 5:
Variation 6:
Method 2:
1.6.2.1.2
1.6.2.1.3
1.6.2.1.4
1.6.2.1.5
1.6.2.1.6
1.6.2.2
1.6.2.3
Variation 1:
Variation 2:
Method 3:
1.6.2.4
Method 4:
1.6.2.4.1
1.6.2.4.4
Variation 1:
Variation 2:
Variation 3:
Variation 4:
1.6.2.5
Method 5:
1.6.2.6
Method 6:
1.6.2.6.1
1.6.2.6.2
Variation 1:
Variation 2:
1.6.2.6.3
Variation 3:
1.6.2.6.4
Variation 4:
Variation 5:
Variation 6:
Variation 7:
Variation 8:
Variation 9:
1.6.2.2.1
1.6.2.2.2
1.6.2.4.2
1.6.2.4.3
1.6.2.6.5
1.6.2.6.6
1.6.2.6.7
1.6.2.6.8
1.6.2.6.9
Preparation of Neutral Iridium(I)±Dienyl Complexes by
Ligand Substitution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From [Ir2(ì-Cl)2(ç4-cod)2] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From [Ir2(ì-Cl)2(ç2-coe)4] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From [Ir2(ì-Cl)2(ç2-coe)4] and Phosphines . . . . . . . . . . . . . . . . . .
From [Ir2(ì-Cl)2(ç2-coe)4] and Ethene . . . . . . . . . . . . . . . . . . . . . . .
From [IrnCln(CO)3n] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From [IrCl3·3H2O] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
630
630
632
632
634
635
635
Preparation of Cationic Iridium(III)±Dienyl Complexes by
Elimination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 636
From [IrH2(OCMe2)2(PPh3)2]X (X = SbF6 or BF4) . . . . . . . . . . . . . . 636
From [Ir2(Cp*)2(ì-Cl)2Cl2] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 637
Preparation of Cationic Iridium(I)±Dienyl Complexes by
Rearrangement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 638
Preparation of Cationic Iridium(III)±Cyclohexadienyl and
Iridium(III)±Cycloheptadienyl Complexes by Elimination . . . . . 640
From [IrH2(OCMe2)2(PPh3)2]BF4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 640
From [Ir(ç4-cod)(L)2]SbF6 (L = phosphine) . . . . . . . . . . . . . . . . . . . 641
Oxo-ç5-cyclohexadienyl Complexes from [Ir2(Cp*)2(ì-Cl)2Cl2]
641
Imino-ç5-cyclohexadienyl Complexes from
[Ir2(Cp*)2(ì-Cl)2Cl2] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 642
Preparation of Cationic Iridium(III)±Cyclohexadienyl
Complexes by Addition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 644
Preparation of (Dienyl)iridium(III) Complexes with Retention
of the Cyclopentadienyl Ligand . . . . . . . . . . . . . . . . . . . . . . . . . . . . 645
Dienyl Hydrides from Borohydride and (Dienyl)iridium Halides 645
Dienyl Hydrides from Reaction of Dienyl Halides and
Zinc/Acetic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 646
Conversion of [Ir2(Cp*)2(ì-Cl)Cl2(ì-H)] into
[Ir2(Cp*)2(ì-H)3]PF6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 647
Conversion of [Ir2(Cp*)2(ì-H)3]PF6 into [Ir(Cp*)H4] . . . . . . . . . . . 648
Dienyl Hydrides from Protonation at Iridium . . . . . . . . . . . . . . . . 649
Dienyl Fluoride Complexes by Ligand Substitution . . . . . . . . . . 650
Dienyl Alkoxide Complexes by Ligand Substitution . . . . . . . . . . 651
Dienyl Acetate Complexes by Ligand Substitution . . . . . . . . . . . 652
Dienyl á-Amino Acidate Complexes by Ligand Substitution . . 652
Science of Synthesis Original Edition Volume 1
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Table of Contents
1.6.2.6.10
1.6.2.6.14
Variation 10:
Variation 11:
Variation 12:
Variation 13:
Variation 14:
1.6.2.6.15
Variation 15:
1.6.2.6.16
Variation 16:
1.6.2.6.17
Variation 17:
Variation 18:
1.6.2.6.11
1.6.2.6.12
1.6.2.6.13
1.6.2.6.18
1.6.2.6.20
Variation 19:
Variation 20:
1.6.2.6.21
Variation 21:
1.6.2.6.22
Variation 22:
1.6.2.6.23
Variation 23:
1.6.2.6.24
Variation 24:
1.6.2.6.25
1.6.2.6.34
Variation 25:
Variation 26:
Variation 27:
Variation 28:
Variation 29:
Variation 30:
Variation 31:
Variation 32:
Variation 33:
Variation 34:
1.6.2.6.35
Variation 35:
1.6.2.6.19
1.6.2.6.26
1.6.2.6.27
1.6.2.6.28
1.6.2.6.29
1.6.2.6.30
1.6.2.6.31
1.6.2.6.32
1.6.2.6.33
Dienyl Triflate (Coordinated) Complexes by Substitution . . . .
Dienyl Hydroxo Complexes by Ligand Substitution . . . . . . . . . .
A Dienyl ì-Oxo Complex by Ligand Substitution . . . . . . . . . . . .
Dienyl Imido Complexes by Ligand Substitution . . . . . . . . . . . . .
654
655
656
656
A Mononuclear (Dienyl)iridium±Nitrosyl Complex by
Ligand Substitution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 657
A Mononuclear (Dienyl)iridium±Aryldiazenido Complex by
Ligand Substitution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 658
A Mononuclear (Dienyl)iridium±Amido Complex by
Ligand Substitution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 659
(Dienyl)iridium±Amine Complexes by Ligand Addition . . . . . . 660
Cationic (Dienyl)iridium±Amine Complexes by
Ligand Addition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 661
Cationic (Dienyl)iridium±Acetonitrile Complexes . . . . . . . . . . . . 662
(Dienyl)iridium±Alkyl Complexes by Substitution of
Alkyl for Halide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 663
(Dienyl)iridium±Alkyl Complexes by Alkylation of a
Dienyl Metalate Anion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 664
(Dienyl)iridium±Alkyl Complexes by Oxidative Addition
of Alkanes to [Ir(Cp*)(PMe3)] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 665
(Dienyl)iridium±Aryl Complexes by Oxidative Addition of
Arenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 666
(Dienyl)iridium±Alkyl Complexes by Oxidative Addition of
Alkyl Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 667
(Dienyl)iridium±Carbon Monoxide Complexes by Substitution 667
(Dienyl)iridium±Carbon Monoxide Complexes by Addition . . 668
Dienyl Chloride Complexes by Oxidative Addition of Chlorine 669
Dienyl Bis(Sulfido) Complexes by Substitution . . . . . . . . . . . . . . 669
Dienyl Phosphine Complexes by Substitution . . . . . . . . . . . . . . . 671
[Ir(Cp*){P(OMe)3}3](ClO4)2 from [Ir2(Cp*)2(ì-Cl)2Cl2] . . . . . . . . . 672
Dienyl Silyl Complexes by Silylation of a Dienyl Metalate Anion 673
Dienyl Bromo Complexes by Substitution . . . . . . . . . . . . . . . . . . . 673
Dienyl Bromo Complexes by Oxidative Addition of Bromine . 674
Dienyl Diselenolate Complexes by Oxidative Addition of
Diselenides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 674
Dienyl Iodo Complexes by Oxidative Addition of Iodine . . . . . . 675
Applications of Product Subclass 2 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 675
1.6.2.7
Method 7:
Conversion of Alkynes and Hexaborane(10) into
Alkenylboranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 675
1.6.3
Product Subclass 3: Iridium±Diene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . 676
Synthesis of Product Subclass 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 677
1.6.3.1
1.6.3.1.1
1.6.3.1.2
1.6.3.2
Method 1:
Variation 1:
Variation 2:
Method 2:
Iridium±Diene Complexes by Ligand Substitution . . . . . . . . . . .
Synthesis of [Ir(ç4-C6H6)(triphos)]BPh4 . . . . . . . . . . . . . . . . . . . . . .
From [Ir2(ì-Cl)2(ç2-coe)4] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Iridium±Diene Complexes by Ligand Elimination . . . . . . . . . . . .
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677
678
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Table of Contents
1.6.3.3.1
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Method 3:
Variation 1:
1.6.3.3.2
Variation 2:
1.6.3.4
1.6.3.5
Method 4:
Method 5:
1.6.3.5.1
Variation 1:
1.6.3.5.2
Variation 2:
1.6.3.5.3
1.6.3.5.9
Variation 3:
Variation 4:
Variation 5:
Variation 6:
Variation 7:
Variation 8:
Variation 9:
1.6.3.5.10
Variation 10:
1.6.3.5.11
1.6.3.5.12
Variation 11:
Variation 12:
1.6.3.5.13
Variation 13:
1.6.3.5.14
Variation 14:
1.6.3.5.15
Variation 15:
Variation 16:
Variation 17:
1.6.3.2.1
1.6.3.2.2
1.6.3.2.3
1.6.3.2.4
1.6.3.3
1.6.3.5.4
1.6.3.5.5
1.6.3.5.6
1.6.3.5.7
1.6.3.5.8
1.6.3.5.16
1.6.3.5.17
Synthesis of [Ir2(ì-Cl)2(ç4-cod)2] . . . . . . . . . . . . . . . . . . . . . . . . . . .
Synthesis of [IrCl(ç4-TFB)2] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Synthesis of [Ir(ç4-cod)2]BF4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Synthesis of [IrH(ç4-1,3-C6H8)(ç4-cod)] . . . . . . . . . . . . . . . . . . . . .
Iridium±Diene Complexes by Addition Reactions . . . . . . . . . . . .
Synthesis of [Ir(Cp*)(ç4-1,3-C6H8)] from
[Ir(Cp*)(ç6-C6H6)](BF4)2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
XXIX
679
680
680
681
682
682
Synthesis of the ç4-Cyclohexadienone Complex
[Ir(Cp*){ç4-C6H5(O)OMe}] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 683
Iridium±Diene Complexes by Rearrangement . . . . . . . . . . . . . . . 684
Preparation of Iridium±Diene Complexes with Retention of
the Diene Ligand . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 685
Synthesis of a (Diene)iridium Dihydride Complex:
cis,trans-[IrH2(ç4-cod)(PMePh2)2]PF6 . . . . . . . . . . . . . . . . . . . . . . . . 685
Synthesis of (Diene)iridium Hydride Complexes from
HX Addition to Iridium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 686
Synthesis of [IrH(ç4-cod)(PPh3)2] . . . . . . . . . . . . . . . . . . . . . . . . . . . 686
Synthesis of [Ir2(ì-OMe)2(ç4-cod)2] . . . . . . . . . . . . . . . . . . . . . . . . . 687
Synthesis of [Ir(hfac)(ç4-cod)] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 688
Synthesis of Iridium±Amine Complexes: [IrCl(bipy)(ç4-TFB)] . 688
Synthesis of [Ir(Tp)(ç4-cod)] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 689
Synthesis of [Ir(ç4-cod)(py)2]PF6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . 690
Synthesis of Iridium±Alkynyl Complexes:
[Ir(CºCPh)(ç4-cod)(PCy3)] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 691
Synthesis of Iridium±Alkyl Complexes:
[Ir(Me)(ç4-1,3-C6H8)2] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 691
Synthesis of [Ir(ç4-cod)(py)(PCy3)]PF6 . . . . . . . . . . . . . . . . . . . . . . . 692
Synthesis of a Phosphinodihydrooxazole Complex:
[Ir(ç4-cod)(NP)]BARF . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 692
Synthesis of a Neutral Phosphine Complex:
[IrCl(ç4-cod)(PPh3)] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 693
Synthesis of Neutral Phosphine Complexes with Retention
of the Diene Ligand: [IrCl(ç4-cod){(±)-Chiraphos}] . . . . . . . . . . . 694
Synthesis of [Ir(ç4-cod)(PPh3)2]BF4 . . . . . . . . . . . . . . . . . . . . . . . . . . 695
Synthesis of [Ir(ç4-cod)(PMe3)3]Cl . . . . . . . . . . . . . . . . . . . . . . . . . . 696
Synthesis of [Ir(ç4-cod){(+)-degusph}]BF4 . . . . . . . . . . . . . . . . . . . 697
Applications of Product Subclass 3 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 698
1.6.3.6
1.6.3.6.1
1.6.3.6.2
1.6.3.6.3
1.6.3.6.4
1.6.3.6.5
1.6.3.6.6
1.6.3.6.7
Method 6:
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Variation 5:
Variation 6:
Variation 7:
Iridium±Diene Complexes as Catalyst Precursors . . . . . . . . . . . .
Hydrogenation of Carbonyl Compounds via
Hydrogen Atom Transfer from Propan-2-ol . . . . . . . . . . . . . . . . .
Hydrogenation of Ketones with Hydrogen . . . . . . . . . . . . . . . . . .
Asymmetric Hydrosilylation of Ketones . . . . . . . . . . . . . . . . . . . . .
Asymmetric Hydrogenation of Imines . . . . . . . . . . . . . . . . . . . . . .
Hydrogenation of Alkenes with [Ir(ç4-cod)(py)(PCy3)]PF6 . . . .
Asymmetric Hydrogenation of Alkenes . . . . . . . . . . . . . . . . . . . . .
Allylic Alkylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Science of Synthesis Original Edition Volume 1
© Georg Thieme Verlag KG
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698
700
703
705
709
710
711
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Table of Contents
1.6.3.6.8
Variation 8:
1.6.4
Product Subclass 4: Iridium±Allyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 714
Isomerization of Allyl Ethers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 712
Synthesis of Product Subclass 4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 715
1.6.4.3.1
Method 1:
Variation 1:
Variation 2:
Method 2:
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Method 3:
Variation 1:
1.6.4.3.2
Variation 2:
1.6.4.1
1.6.4.1.1
1.6.4.1.2
1.6.4.2
1.6.4.2.1
1.6.4.2.2
1.6.4.2.3
1.6.4.2.4
1.6.4.3
Preparation of Iridium±Allyl Complexes by Ligand Substitution
From Iridium Halides and Grignard or Organolithium Reagents
Synthesis of the Cyclopropenyl Complex [Ir(ç3-C3t-Bu3)(CO)3]
Preparation of Iridium±Allyl Complexes by Addition . . . . . . . . .
From Iridium(I) Precursors and Allyl Halides . . . . . . . . . . . . . . . . .
From [Ir2(ì-Cl)2(ç2-coe)4] and Allylbenzene . . . . . . . . . . . . . . . . .
From Diene Insertion into Ir-H Bonds . . . . . . . . . . . . . . . . . . . . . .
From Nucleophilic Attack on a ç1-Allenyl Ligand . . . . . . . . . . . .
Preparation of Iridium±Allyl Complexes by Elimination . . . . . .
715
715
716
717
717
718
718
719
720
From [Ir2(Cp*)2(ì-Cl)2Cl2] and Dienes in the Presence of
Alcohol and Base . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 720
From [Ir2(Cp*)2(ì-Cl)2Cl2], Silver(I) Salts, and an Alkene . . . . . . 721
Applications of Product Subclass 4 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 722
Nucleophilic Attack on ð-Allyl Intermediates . . . . . . . . . . . . . . . 722
1.6.4.4
Method 4:
1.6.5
Product Subclass 5: Iridium±Alkyne Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . 722
Synthesis of Product Subclass 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 723
1.6.5.1
Method 1:
Preparation of Iridium±Alkyne Complexes by
Ligand Substitution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 723
Preparation of Iridium±Alkyne Complexes by Addition . . . . . . 724
1.6.5.2
Method 2:
1.6.6
Product Subclass 6: Iridium±Alkene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . 725
Synthesis of Product Subclass 6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 726
1.6.6.1
Method 1:
1.6.6.2
Method 2:
Method 3:
1.6.6.3
Preparation of Iridium±Alkene Complexes by
Ligand Substitution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 726
Preparation of Iridium±Alkene Complexes by Addition . . . . . . 727
Preparation of Iridium±Alkene Complexes by Elimination . . . . 728
Applications of Product Subclass 6 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 729
Iridium±Alkene Complexes in Catalysis . . . . . . . . . . . . . . . . . . . . . 729
1.6.6.4
Method 4:
1.6.7
Product Subclass 7: Iridium±Carbene Complexes . . . . . . . . . . . . . . . . . . . . . . . . 729
Synthesis of Product Subclass 7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 730
1.6.7.1
Method 1:
1.6.7.1.1
Variation 1:
1.6.7.1.2
Variation 2:
1.6.7.1.3
Variation 3:
1.6.7.2
Method 2:
Preparation of Iridium±Carbene Complexes by
Ligand Substitution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 730
From [Ir(R1C=CR1CR1=CR1)(NCMe)2(PPh3)2]BF4 and
But-3-yn-1-ol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 730
A Vinylidene Complex from [Ir{N(SiMe2CH2PPh2)2}(ç2-coe)]
and Acetylene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 731
A Vinylidene Complex from [Ir2(ì-Cl)2(ç2-coe)4] and
Sodium/1-Chloro-2-methylprop-1-ene . . . . . . . . . . . . . . . . . . . . . 731
Preparation of Iridium±Carbene Complexes by Addition . . . . . 732
Science of Synthesis Original Edition Volume 1
© Georg Thieme Verlag KG
Table of Contents
1.6.7.2.1
Variation 1:
1.6.7.2.2
Variation 2:
1.6.7.3
1.6.7.3.4
Method 3:
Variation 1:
Variation 2:
Variation 3:
Variation 4:
1.6.7.4
Method 4:
1.6.8
Product Subclass 8: Iridium±Carbyne Complexes . . . . . . . . . . . . . . . . . . . . . . . . 736
1.6.7.3.1
1.6.7.3.2
1.6.7.3.3
From [IrCl(CO)(PPh3)2] and
(Chloromethylene)dimethylammonium Chloride . . . . . . . . . . .
From [IrClH(OTf)(CO)(PPh3)2] and
Benzylidyne(methyl)ammonium Triflate . . . . . . . . . . . . . . . . . . . .
Preparation of Iridium±Carbene Complexes by Elimination . .
From [IrCl(CO)(PPh3)2] and Electron-Rich Alkenes . . . . . . . . . . .
From [IrCl2H(PPh3)3] and Bis(trichloromethyl)mercury(II) . . . .
From [IrClH2(P-iPr3)2] and Acetylene . . . . . . . . . . . . . . . . . . . . . . . .
XXXI
732
733
733
733
734
734
An Iridium±Allenylidene Complex from
[Ir(CºCCPh2OH)ClH(P-iPr3)2] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 735
Preparation of Iridium±Vinylidene Complexes by
Rearrangement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 736
Synthesis of Product Subclass 8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 736
Product Class 7: Organometallic Complexes of Iron
G. R. Stephenson
1.7
1.7
Product Class 7: Organometallic Complexes of Iron . . . . . . . . . . . . . . . . . . . . . . 745
1.7.1
Product Subclass 1: Iron±Arene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 749
Synthesis of Product Subclass 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 749
1.7.1.2.1
Method 1:
Method 2:
Variation 1:
1.7.1.2.2
Variation 2:
1.7.1.1
1.7.1.2
1.7.1.2.3
Variation 3:
1.7.1.2.4
Variation 4:
Variation 5:
1.7.1.2.5
Direct Complexation of Arenes . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Modification of ç6-Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Replacement of Chloride in Chlorobenzene Complexes by
Nucleophiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Use of Palladium-Catalyzed Coupling in the Presence
of Cationic Iron±Cyclopentadienyl Complexes . . . . . . . . . . . . . .
749
750
751
752
Use of Nucleophilic Complexes Obtained by Deprotonation
of Arene±Cyclopentadienyliron Complexes . . . . . . . . . . . . . . . . . 752
Nucleophile Addition to a Carbonyl Ligand . . . . . . . . . . . . . . . . . 753
Hydrogenation of Ligands in the Presence of
Cationic Iron±Cyclopentadienyl Complexes . . . . . . . . . . . . . . . . . 753
Applications of Product Subclass 1 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 753
Metal Removal To Give Organic Products . . . . . . . . . . . . . . . . . . . 753
1.7.1.3
Method 3:
1.7.2
Product Subclass 2: Iron±Dienyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 755
Synthesis of Product Subclass 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 755
1.7.2.1
1.7.2.1.1
1.7.2.1.2
1.7.2.1.3
1.7.2.2
1.7.2.2.1
1.7.2.2.2
Method 1:
Variation 1:
Variation 2:
Variation 3:
Method 2:
Variation 1:
Variation 2:
Direct Complexation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Reaction of Cyclopentadienyl Anions with Iron Salts . . . . . . . . .
Transfer of Cyclopentadienyliron . . . . . . . . . . . . . . . . . . . . . . . . . . .
From Neutral Cyclopentadiene Derivatives . . . . . . . . . . . . . . . . .
Modification of ç5-Cyclopentadienyl Complexes . . . . . . . . . . . .
Friedel±Crafts Acylation of Ferrocene Complexes . . . . . . . . . . .
Metalation of Ferrocene Complexes . . . . . . . . . . . . . . . . . . . . . . . .
Science of Synthesis Original Edition Volume 1
© Georg Thieme Verlag KG
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757
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758
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1.7.2.2.3
Variation 3:
Variation 4:
Variation 5:
Variation 6:
1.7.2.2.4
1.7.2.2.5
1.7.2.2.6
1.7.2.3
1.7.2.3.1
1.7.2.3.2
1.7.2.4
1.7.2.5
1.7.2.5.1
1.7.2.5.2
1.7.2.6
1.7.2.7
1.7.2.8
1.7.2.9
1.7.2.9.1
1.7.2.9.2
1.7.2.10
1.7.2.10.1
1.7.2.10.2
1.7.2.10.3
1.7.2.11
Method 3:
Variation 1:
Variation 2:
Method 4:
Method 5:
Variation 1:
Variation 2:
Method 6:
Method 7:
Method 8:
Method 9:
Variation 1:
Variation 2:
Method 10:
Variation 1:
Variation 2:
Variation 3:
Method 11:
1.7.2.13.2
Variation 1:
Variation 2:
Method 12:
Method 13:
Variation 1:
Variation 2:
1.7.2.13.3
Variation 3:
1.7.2.11.1
1.7.2.11.2
1.7.2.12
1.7.2.13
1.7.2.13.1
Modification of Substituents on Ferrocene Complexes . . . . . . 758
Redox Chemistry at the Metal of Ferrocene Complexes . . . . . . 759
Protonation at Iron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 759
Manipulation of Di-ì-carbonyldicarbonylbis(ç5-cyclopentadienyl)diiron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 759
Preparation by Hydride Abstraction . . . . . . . . . . . . . . . . . . . . . . . . 760
Regioisomer Preparation without Rearrangement . . . . . . . . . . . 761
Regioisomer Preparation with Rearrangement . . . . . . . . . . . . . . 762
Preparation from ç4-Triene Complexes with Electrophiles . . . 762
Preparation from Dienol Complexes with Acid . . . . . . . . . . . . . . 763
Without Rearrangement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 764
With Rearrangement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 765
Preparation by Demethoxylation in Acid . . . . . . . . . . . . . . . . . . . . 765
Preparation by Oxidation with Thallium(III) Salts . . . . . . . . . . . . 767
Preparation from Dienone Complexes . . . . . . . . . . . . . . . . . . . . . . 767
Preparation from ç6-Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 768
Nucleophile Addition to ç6-Complexes at the ð-System . . . . . 768
Dealkoxylation of ç6-Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . 770
Nucleophile Addition to ç5-Complexes . . . . . . . . . . . . . . . . . . . . . 770
Addition at the ð-System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 770
Addition next to the ð-System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 770
Addition at a Carbonyl Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 771
Access to Salts by a Sequence of Nucleophile Addition
and Leaving-Group Removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 771
Without Rearrangement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 772
With Rearrangement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 773
Opening Cyclopropane Rings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 774
Preparation of Nonracemic Complexes . . . . . . . . . . . . . . . . . . . . . 774
From Ferrocene Complexes by Asymmetric Induction . . . . . . . 774
From Complexes Originating from Resolution or
Asymmetric Induction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 775
From Complexes Originating from Biological Sources . . . . . . . 776
Applications of Product Subclass 2 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 777
Metal Removal To Give Organic Products . . . . . . . . . . . . . . . . . . . 777
From Ferrocene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 777
From Cationic ç5-Ligated Tricarbonyliron Complexes . . . . . . . . 777
From ç5-Cyclopentadienyl±Iron Complexes Formed by
Nucleophilic Addition to ç6-Complexes . . . . . . . . . . . . . . . . . . . . . 778
1.7.2.14.3
Method 14:
Variation 1:
Variation 2:
Variation 3:
1.7.3
Product Subclass 3: Iron±Diene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 778
1.7.2.14
1.7.2.14.1
1.7.2.14.2
Synthesis of Product Subclass 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 778
1.7.3.1
1.7.3.1.1
1.7.3.1.2
1.7.3.1.3
1.7.3.1.4
Method 1:
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Preparation by Complexation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From Dienes without Rearrangement . . . . . . . . . . . . . . . . . . . . . .
From Dienes with Rearrangement . . . . . . . . . . . . . . . . . . . . . . . . . .
From Dienes and Alkynes by Reaction with ç1-Complexes . . .
From Cyclohexadienones by Reduction . . . . . . . . . . . . . . . . . . . . .
Science of Synthesis Original Edition Volume 1
© Georg Thieme Verlag KG
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Table of Contents
1.7.3.1.5
1.7.3.1.6
1.7.3.1.7
1.7.3.1.8
1.7.3.1.9
1.7.3.1.10
1.7.3.1.11
1.7.3.2
1.7.3.2.1
1.7.3.2.2
1.7.3.2.3
1.7.3.3
1.7.3.4
1.7.3.4.1
1.7.3.4.2
1.7.3.4.3
1.7.3.4.4
1.7.3.4.5
1.7.3.4.6
1.7.3.5
1.7.3.6
1.7.3.6.1
1.7.3.6.2
1.7.3.6.3
1.7.3.6.4
1.7.3.6.5
1.7.3.6.6
1.7.3.6.7
1.7.3.6.8
1.7.3.6.9
1.7.3.6.10
1.7.3.6.11
1.7.3.7
1.7.3.8
1.7.3.8.1
1.7.3.8.2
1.7.3.8.3
1.7.3.9
1.7.3.9.1
1.7.3.9.2
1.7.3.9.3
1.7.3.9.4
1.7.3.9.5
Variation 5:
Variation 6:
Variation 7:
Variation 8:
Variation 9:
Variation 10:
Variation 11:
Method 2:
Variation 1:
Variation 2:
Variation 3:
Method 3:
Method 4:
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Variation 5:
Variation 6:
Method 5:
Method 6:
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Variation 5:
Variation 6:
Variation 7:
Variation 8:
Variation 9:
Variation 10:
Variation 11:
Method 7:
Method 8:
Variation 1:
Variation 2:
Variation 3:
Method 9:
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Variation 5:
XXXIII
From Dihydrothiophene 1,1-Dioxides . . . . . . . . . . . . . . . . . . . . . . .
From Allyl Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From Dihalides, Allyl Halides, and Phosphate Esters . . . . . . . . .
From Pyrones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From Dimethylcyclopropenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From Vinylcyclopropanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From Allenes via Trimethylenemethane Lactones . . . . . . . . . . .
Preparation from ç3,ç1-Complexes . . . . . . . . . . . . . . . . . . . . . . . . .
From Ferralactone Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From ç3,ç1-Allenyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Nucleophile Addition to Cationic ç3,ç1-Carbene Complexes .
Cyclodimerization of ç2-Ligands . . . . . . . . . . . . . . . . . . . . . . . . . . .
Nucleophile Addition to ç5-Complexes at the ð-System . . . . .
Cyclohexadienyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Cycloheptadienyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Cyclooctadienyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acyclic Dienyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
In Situ Generation of Acyclic Dienyl Complexes . . . . . . . . . . . . .
Cyclopentadienyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Metal-Centered Reduction of ç5-Complexes at the ð-System
Modification of ç4-Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
By Acylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
By Lithiation and Addition of Electrophiles . . . . . . . . . . . . . . . . . .
By Palladium Coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Nucleophile Addition to ç4-Complexes at the ð-System . . . . .
Nucleophile Addition to ç4-Complexes at a Carbonyl Ligand .
Nucleophile Addition to ç4-Complexes next to the ð-System
Reactions of Enolates and Silyl Enol Ethers . . . . . . . . . . . . . . . . . .
Epoxide Formation and Cyclopropanation next to
the ð-System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Diol Synthesis next to the ð-System . . . . . . . . . . . . . . . . . . . . . . . .
Cycloaddition Reactions next to the ð-System . . . . . . . . . . . . . .
Functionalization of Cycloheptatriene Complexes . . . . . . . . . . .
Complexation of Heterodienes . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Additional Methods for the Formation of ç4-Complexes . . . . .
Alkylation of ç3-Anions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From Pentacarbonyliron by Nucleophile Addition at Carbonyl
Exchange of Carbonyl for Phosphines, Phosphites,
and Nitrosonium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Preparation of Nonracemic Complexes . . . . . . . . . . . . . . . . . . . . .
Asymmetric Complexation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Asymmetric Modification of Prochiral ç4-Complexes . . . . . . . .
By Asymmetric Induction and Kinetic Resolution with
782
782
782
783
783
784
784
784
785
785
786
786
787
787
794
795
795
797
799
799
799
799
800
801
802
802
803
806
807
808
808
810
810
811
811
812
812
813
813
815
ç5-Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 816
Classical Resolution of Chiral ç4-Complexes . . . . . . . . . . . . . . . . . 817
Kinetic Resolution of Chiral ç4-Complexes . . . . . . . . . . . . . . . . . . 818
Science of Synthesis Original Edition Volume 1
© Georg Thieme Verlag KG
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Applications of Product Subclass 3 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 818
Metal Removal To Give Organic Products . . . . . . . . . . . . . . . . . . .
Decomplexation without Ligand Modification . . . . . . . . . . . . . .
Decomplexation with Ligand Modification . . . . . . . . . . . . . . . . . .
Reactions next to ç3-Complexes, Followed by Rearrangement
1.7.3.11
Method 10:
Variation 1:
Variation 2:
Method 11:
1.7.4
Product Subclass 4: Iron±Allyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 826
1.7.3.10
1.7.3.10.1
1.7.3.10.2
818
818
822
826
Synthesis of Product Subclass 4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 826
1.7.4.1
1.7.4.1.1
1.7.4.1.2
1.7.4.1.3
Method 1:
Variation 1:
Variation 2:
Variation 3:
1.7.4.2
Method 2:
1.7.4.3
Method 3:
Variation 1:
Variation 2:
Variation 3:
Method 4:
Variation 1:
Variation 2:
Method 5:
Method 6:
Variation 1:
Variation 2:
Method 7:
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Variation 5:
Method 8:
1.7.4.3.1
1.7.4.3.2
1.7.4.3.3
1.7.4.4
1.7.4.4.1
1.7.4.4.2
1.7.4.5
1.7.4.6
1.7.4.6.1
1.7.4.6.2
1.7.4.7
1.7.4.7.1
1.7.4.7.2
1.7.4.7.3
1.7.4.7.4
1.7.4.7.5
1.7.4.8
Protonation of Diene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . .
From ç2-Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From ç4-Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
During Direct Complexation of Allyl Alcohols and Dienes
in the Presence of Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Preparation by Leaving-Group Displacement from
ç2-Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Preparation by Opening Vinyl Epoxides and Cyclopropanes . .
From Epoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From Aziridines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From Cyclopropanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Nucleophile Addition at a Complexed ð-System . . . . . . . . . . . .
Nucleophile Addition to ç4-Complexes . . . . . . . . . . . . . . . . . . . . .
Nucleophile Addition to ç5-Complexes . . . . . . . . . . . . . . . . . . . . .
Nucleophile Addition to ç3-Complexes next to the ð-System
Nucleophile Addition at a Carbonyl Ligand . . . . . . . . . . . . . . . . . .
Nucleophile Addition to ç4-Complexes . . . . . . . . . . . . . . . . . . . . .
Nucleophile Addition to ç2,ç2-Complexes . . . . . . . . . . . . . . . . . .
Additional Methods for the Formation of ç3-Complexes . . . . .
From ç5- to ç3-Diene Complexes by Carbonyl Insertion . . . . . .
Alkene Insertion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From ç4-Vinylketene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . .
Reductive Methods To Make Anionic ç3-Complexes . . . . . . . . .
Exchange of Carbonyl for Nitrosonium . . . . . . . . . . . . . . . . . . . . .
Preparation of Nonracemic Complexes . . . . . . . . . . . . . . . . . . . . .
826
827
827
827
827
828
828
830
830
830
830
831
832
833
833
834
834
834
834
835
835
835
835
Applications of Product Subclass 4 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 836
Metal Removal To Give Organic Products . . . . . . . . . . . . . . . . . . . 836
1.7.4.9
Method 9:
1.7.5
Product Subclass 5: Iron±Alkene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 839
Synthesis of Product Subclass 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 839
1.7.5.1
1.7.5.1.1
1.7.5.1.2
1.7.5.1.3
1.7.5.2
1.7.5.2.1
1.7.5.2.2
1.7.5.2.3
Method 1:
Variation 1:
Variation 2:
Variation 3:
Method 2:
Variation 1:
Variation 2:
Variation 3:
Direct Complexation of Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Ligand Exchange with a Butene Complex . . . . . . . . . . . . . . . . . . .
Reaction with Nonacarbonyldiiron . . . . . . . . . . . . . . . . . . . . . . . . .
Reaction with Pentacarbonyliron . . . . . . . . . . . . . . . . . . . . . . . . . . .
Preparation by Protonation of ç1-Complexes . . . . . . . . . . . . . . .
Protonation of ç1-Allyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . .
Removal of Leaving Groups from ç1-Alkyl Complexes . . . . . . .
Protonation at Iron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Science of Synthesis Original Edition Volume 1
© Georg Thieme Verlag KG
839
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840
840
841
841
Table of Contents
1.7.5.3
1.7.5.3.1
1.7.5.3.2
1.7.5.3.3
1.7.5.3.4
1.7.5.4
1.7.5.4.1
1.7.5.4.2
1.7.5.4.3
1.7.5.5
Method 3:
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Method 4:
Variation 1:
Variation 2:
Variation 3:
Method 5:
XXXV
Reactions of ç1-Allyl Complexes with Electrophiles . . . . . . . . . .
Reaction with Aldehydes and Ketones in the Presence of
a Lewis Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Reaction with Activated Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . .
Reaction with ç2-Alkene Complexes . . . . . . . . . . . . . . . . . . . . . . . .
Reaction with ç5-Dienyl Complexes . . . . . . . . . . . . . . . . . . . . . . . .
Nucleophile Addition at a Complexed ð-System . . . . . . . . . . . .
Nucleophile Addition to ç3-Complexes . . . . . . . . . . . . . . . . . . . . .
Nucleophile Addition to ç4-Complexes . . . . . . . . . . . . . . . . . . . . .
Nucleophile Addition to ç5-Complexes . . . . . . . . . . . . . . . . . . . . .
Preparation of Nonracemic Complexes . . . . . . . . . . . . . . . . . . . . .
841
841
842
843
843
843
843
843
844
844
Applications of Product Subclass 5 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 845
Metal Removal To Give Organic Products . . . . . . . . . . . . . . . . . . . 845
1.7.5.6
Method 6:
1.7.6
Product Subclass 6: Iron±Carbene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 846
Synthesis of Product Subclass 6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 846
1.7.6.1
1.7.6.2
1.7.6.3
1.7.6.3.1
1.7.6.3.2
1.7.6.4
1.7.6.5
1.7.6.6
Method 1:
Method 2:
Method 3:
Variation 1:
Variation 2:
Method 4:
Method 5:
Method 6:
Preparation by the Fischer Carbene Method . . . . . . . . . . . . . . . .
Removal of Leaving Groups from Metal±Alkyl Complexes . . .
Modification of Other Carbene Complexes . . . . . . . . . . . . . . . . .
Exchange of Substituents at the Carbene Complex . . . . . . . . . .
846
847
848
848
Reactions at Functional Groups Adjacent to
the Carbene Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Preparation by Ring Expansion . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Preparation of Bridging Carbene Complexes . . . . . . . . . . . . . . . .
Preparation of Nonracemic Complexes . . . . . . . . . . . . . . . . . . . . .
848
849
849
851
Applications of Product Subclass 6 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 852
Cyclopropanation by Transfer of Diazoesters . . . . . . . . . . . . . . . .
C-H Insertion Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Cyclization with Alkynes To Form Naphthols . . . . . . . . . . . . . . . .
Removal of the Metal by Oxidation . . . . . . . . . . . . . . . . . . . . . . . . .
1.7.6.10
Method 7:
Method 8:
Method 9:
Method 10:
1.7.7
Product Subclass 7: Iron±Alkyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 853
1.7.6.7
1.7.6.8
1.7.6.9
852
852
852
853
Synthesis of Product Subclass 7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 853
1.7.7.1
1.7.7.2
1.7.7.3
1.7.7.4
1.7.7.4.1
1.7.7.4.2
1.7.7.4.3
1.7.7.4.4
1.7.7.5
1.7.7.5.1
1.7.7.5.2
1.7.7.6
1.7.7.7
Method 1:
Method 2:
Method 3:
Method 4:
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Method 5:
Variation 1:
Variation 2:
Method 6:
Method 7:
Metal Addition to Organic Electrophiles . . . . . . . . . . . . . . . . . . . .
Metal Addition to Organic Nucleophiles/Lewis Bases . . . . . . . .
Nucleophile Addition to ç2-Alkene Complexes . . . . . . . . . . . . . .
Additional Methods for the Formation of ç1-Alkyl Complexes
Nucleophile Addition to ç1-Carbene Complexes . . . . . . . . . . . . .
Nucleophile Addition to ç2-Alkyne Complexes . . . . . . . . . . . . . .
Nucleophile Addition to Carbonyl Complexes . . . . . . . . . . . . . . .
Deprotonation of ç2-Alkene Complexes . . . . . . . . . . . . . . . . . . . .
Reactions of Allyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
ç1-Allyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
ç3-Allyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Modification of Ligands in ç1-Complexes . . . . . . . . . . . . . . . . . . .
Preparation of Nonracemic Complexes . . . . . . . . . . . . . . . . . . . . .
Science of Synthesis Original Edition Volume 1
© Georg Thieme Verlag KG
853
854
854
855
855
855
855
856
856
856
857
857
859
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Table of Contents
Applications of Product Subclass 7 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 860
1.7.7.8
1.7.7.8.1
1.7.7.8.2
1.7.7.8.3
1.7.7.8.4
1.7.7.8.5
1.7.7.8.6
1.7.7.9
1.7.7.9.1
1.7.7.9.2
1.7.7.9.3
1.7.7.10
1.7.7.10.1
1.7.7.10.2
1.7.7.10.3
1.7.7.11
1.7.7.11.1
1.7.7.11.2
1.7.8
1.7.8
Method 8:
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Variation 5:
Variation 6:
Method 9:
Variation 1:
Variation 2:
Variation 3:
Method 10:
Variation 1:
Variation 2:
Variation 3:
Method 11:
Variation 1:
Variation 2:
Oxidation of ç1-Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Metal Removal To Generate a Carboxylic Acid . . . . . . . . . . . . . .
Metal Removal To Generate an Ester . . . . . . . . . . . . . . . . . . . . . . .
Metal Removal To Generate an Amide . . . . . . . . . . . . . . . . . . . . . .
Metal Removal To Generate Alkyl Bromides or Epoxides . . . . .
Metal Removal To Generate Cyclic Ketones . . . . . . . . . . . . . . . . .
Metal Removal with Transmetalation to Mercury . . . . . . . . . . . .
860
860
861
862
862
863
863
Additional Methods for Decomplexation of
ç1-Alkyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Disproportionation of ç1-Products . . . . . . . . . . . . . . . . . . . . . . . . .
Photochemical Dimerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Asymmetric Cycloaddition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Formation and Reaction of Oxyallyl Cation Complexes . . . . . .
[4 + 3] Cycloaddition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
[2 + 3] Cycloaddition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Electrophilic Substitution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Application of Collmans Reagent . . . . . . . . . . . . . . . . . . . . . . . . . .
Cyclization to Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Reductions with the Tetracarbonylhydroferrate Complex . . . .
864
864
864
864
864
864
865
865
865
866
867
Product Subclass 8: Ferrocenes
M. Perseghini and A. Togni
Product Subclass 8: Ferrocenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 889
Synthesis of Product Subclass 8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 890
1.7.8.1
Method 1:
1.7.8.1.1
Variation 1:
1.7.8.1.2
Variation 2:
1.7.8.1.3
1.7.8.1.4
1.7.8.2
1.7.8.3
1.7.8.3.1
1.7.8.3.2
1.7.8.3.3
1.7.8.3.4
1.7.8.4
1.7.8.5
1.7.8.6
Variation 3:
Variation 4:
Method 2:
Method 3:
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Method 4:
Method 5:
Method 6:
Monosubstituted and 1,1¢-Disubstituted Ferrocenes via
Metalated Intermediates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 890
Synthesis of Halogenated Ferrocenes . . . . . . . . . . . . . . . . . . . . . . 890
Synthesis of Hydroxyferrocene and 1,1¢-Dihydroxyferrocene
via the Ferroceneboronic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Synthesis of Aminoferrocene and 1,1¢-Diaminoferrocene . . . .
Synthesis of Carboxyferrocene, Formylferrocene,
1,1¢-Dicarboxyferrocene, and 1,1¢-Diformylferrocene . . . . . . . .
Acylferrocenes under Friedel±Crafts Conditions . . . . . . . . . . . . .
894
895
Chiral 1-Ferrocenylalkyl Alcohols
and 1-Ferrocenylalkylamines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Via Stereoselective Alkylation of Formylferrocene . . . . . . . . . . .
Via Stereoselective Reduction of Acyl Intermediates . . . . . . . .
Via Enzymatic Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
895
896
896
897
Via Racemate Resolution: Preparation of (R)- and
(S)-1-Ferrocenyl-N,N-dimethylethylamine . . . . . . . . . . . . . . . . . . .
Chiral (4,5-Dihydrooxazol-2-yl)ferrocenes . . . . . . . . . . . . . . . . . .
Chiral Ferrocenyl Acetals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Chiral Ferrocenyl Sulfoxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
897
898
900
902
Science of Synthesis Original Edition Volume 1
© Georg Thieme Verlag KG
891
892
Table of Contents
1.7.8.7
Method 7:
1.7.8.7.1
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Method 8:
1.7.8.7.2
1.7.8.7.3
1.7.8.7.4
1.7.8.8
1.7.8.9
1.7.8.10
1.7.8.10.1
1.7.8.10.2
1.7.8.10.3
1.7.8.10.4
1.7.8.10.5
1.7.8.10.6
1.7.8.11
Method 9:
Method 10:
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Variation 5:
Variation 6:
Method 11:
XXXVII
Chiral 1,2-Disubstituted Ferrocenes by
Diastereoselective Functionalization . . . . . . . . . . . . . . . . . . . . . . .
From 1-Ferrocenyl-N,N-dimethylethylamine . . . . . . . . . . . . . . . .
From (4,5-Dihydrooxazol-2-yl)ferrocenes . . . . . . . . . . . . . . . . . . .
From Chiral Ferrocenyl Acetals . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From Chiral Ferrocenyl Sulfoxides . . . . . . . . . . . . . . . . . . . . . . . . . .
903
903
907
908
909
Chiral 1,2-Disubstituted Ferrocenes via
Enantioselective Sparteine-Mediated Lithiation . . . . . . . . . . . . .
1,1¢,2-Trisubstituted Ferrocenes (BPPFA Ligand Type) . . . . . . . .
Tetra- to Decasubstituted Ferrocenes . . . . . . . . . . . . . . . . . . . . . .
From 1,1¢-Bis(1-aminoalkyl)ferrocenes . . . . . . . . . . . . . . . . . . . . . .
From 1,1¢-Bis(4,5-dihydrooxazol-2-yl)ferrocenes . . . . . . . . . . . .
Via Enantioselective Sparteine-Mediated Lithiation . . . . . . . . . .
910
911
913
913
915
916
Synthesis of 4-(Dimethylamino)pyridine Analogues
via Racemate Resolution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From Chiral Fulvene Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From Fully Substituted Cyclopentadienyl Salts . . . . . . . . . . . . . .
Chiral Biferrocenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
916
917
919
921
Applications of Product Subclass 8 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 923
1.7.8.12
1.7.8.13
1.7.8.14
1.7.8.15
1.7.8.16
Method 12:
Method 13:
Method 14:
Method 15:
Method 16:
Catalytic Enantioselective Hydrogenation . . . . . . . . . . . . . . . . . .
Catalytic Enantioselective Hydroboration . . . . . . . . . . . . . . . . . . .
Catalytic Enantioselective Hydrosilylation . . . . . . . . . . . . . . . . . .
Catalytic Enantioselective Allylic Substitution . . . . . . . . . . . . . . .
Catalytic Enantioselective Aldol Reactions . . . . . . . . . . . . . . . . . .
923
923
924
924
924
Product Class 8: Organometallic Complexes of Ruthenium
N. Chatani
1.8
1.8
Product Class 8: Organometallic Complexes of Ruthenium . . . . . . . . . . . . . . . 931
1.8.1
Product Subclass 1: Ruthenium±Arene Complexes . . . . . . . . . . . . . . . . . . . . . . . 931
Synthesis of Product Subclass 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 932
1.8.1.1
1.8.1.1.1
1.8.1.1.2
1.8.1.2
1.8.1.2.1
1.8.1.2.2
Method 1:
Variation 1:
Variation 2:
Method 2:
Variation 1:
Variation 2:
Preparation of Ruthenium(II)±Arene Complexes . . . . . . . . . . . .
From Dienes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
By Ligand Exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Preparation of Ruthenium(0)±Arene Complexes . . . . . . . . . . . .
From Ruthenium(II) Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . .
By Ligand Exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
932
933
934
934
935
936
Applications of Product Subclass 1 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 937
Reactions Involving Ruthenium±Arene Complexes . . . . . . . . . . 937
1.8.1.3
Method 3:
1.8.2
Product Subclass 2: Ruthenium±Cyclopentadienyl and
Ruthenium±Pentadienyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 939
Synthesis of Product Subclass 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 941
1.8.2.1
Method 1:
Preparation of Ruthenium±Cyclopentadienyl Complexes . . . . 941
Science of Synthesis Original Edition Volume 1
© Georg Thieme Verlag KG
XXXVIII
Table of Contents
1.8.2.1.1
Variation 1:
Variation 2:
Variation 3:
Variation 4:
Method 2:
1.8.2.1.2
1.8.2.1.3
1.8.2.1.4
1.8.2.2
From Cyclopentadienes (CpH) . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
From Organometallic Cyclopentadienyl Reagents (MCp) . . . .
By Ligand Exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
By Ligand Substitution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
942
944
945
946
Preparation of Cationic Ruthenium±Cyclopentadienyl
Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 946
Applications of Product Subclass 2 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 947
Reactions with Alkyllithium Reagents . . . . . . . . . . . . . . . . . . . . . . 947
Electrophilic Substitution (Friedel±Crafts-type Reaction) . . . . 947
Preparation of Ruthenium±Vinylidene±Cyclopentadienyl
Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 948
1.8.2.5
Method 3:
Method 4:
Method 5:
1.8.3
Product Subclass 3: Ruthenium±Diene Complexes . . . . . . . . . . . . . . . . . . . . . . . 949
1.8.2.3
1.8.2.4
Synthesis of Product Subclass 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 951
1.8.3.1
Method 1:
Preparation of Ruthenium±Diene Complexes by
Ligand Exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 951
Applications of Product Subclass 3 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 951
Reactions Involving Ruthenium±Diene Complexes . . . . . . . . . . 951
1.8.3.2
Method 2:
1.8.4
Product Subclass 4: Ruthenium±Allyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . 952
Synthesis of Product Subclass 4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 953
1.8.4.1
Method 1:
Preparation of Ruthenium±Allyl Complexes . . . . . . . . . . . . . . . . . 953
Applications of Product Subclass 4 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 954
Reactions Involving Ruthenium±Allyl Complexes . . . . . . . . . . . . 954
1.8.4.2
Method 2:
1.8.5
Product Subclass 5: Ruthenium±Alkyne Complexes . . . . . . . . . . . . . . . . . . . . . . 956
Synthesis of Product Subclass 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 959
1.8.5.1
Method 1:
Preparation of Ruthenium±Alkyne Complexes by Irradiation . 959
Applications of Product Subclass 5 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 959
Reactions Involving Ruthenium±Alkyne Complexes . . . . . . . . . 959
1.8.5.2
Method 2:
1.8.6
Product Subclass 6: Ruthenium±Alkene Complexes . . . . . . . . . . . . . . . . . . . . . . 963
Synthesis of Product Subclass 6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 965
1.8.6.1
1.8.6.2
Method 1:
Method 2:
Preparation of Ruthenium(II)±Alkene Complexes . . . . . . . . . . . . 965
Preparation of Ruthenium(0)±Alkene Complexes . . . . . . . . . . . 965
Applications of Product Subclass 6 in Organic Synthesis . . . . . . . . . . . . . . . . . . . . 967
1.8.6.3
Method 3:
Reactions Involving Ruthenium±Alkene Complexes . . . . . . . . . 967
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© Georg Thieme Verlag KG
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Table of Contents
Product Class 9: Organometallic Complexes of Osmium
J. Gonzalez and W. D. Harman
1.9
1.9
Product Class 9: Organometallic Complexes of Osmium . . . . . . . . . . . . . . . .
973
1.9.1
Product Subclass 1: Osmium±ç -Arene and ±ç -Heteroarene Complexes
977
Synthesis of Product Subclass 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
981
2
1.9.1.1
Method 1:
1.9.1.2
Method 2:
2
Exchange of a Trifluoromethanesulfonate Anion for
an Organic Ligand . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Electrophilic Aromatic Substitution on the Ligand . . . . . . . . . .
981
983
Applications of Product Subclass 1 in Organic Synthesis . . . . . . . . . . . . . . . . . . .
984
Electrophilic Addition and Substitution . . . . . . . . . . . . . . . . . . . .
Sequential Addition of Electrophiles and Nucleophiles . . . . .
[4 + 2]-Cycloaddition Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . .
1,3-Dipolar Cycloadditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
984
987
990
993
1.9.1.4.3
Method 3:
Method 4:
Variation 1:
Variation 2:
Variation 3:
1.9.1.5
Method 5:
1.9.2
Product Subclass 2: Osmium±Allyl Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . 1003
1.9.1.3
1.9.1.4
1.9.1.4.1
1.9.1.4.2
Michael±Michael Ring Closures and
Related Annulation Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 997
Addition of Nucleophiles to S-Alkylthiophenium Complexes 1002
Synthesis of Product Subclass 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1003
1.9.2.1
1.9.2.2
Method 1:
Method 2:
Elimination of Labile Allylic Substituents . . . . . . . . . . . . . . . . . . . 1003
Addition of Electrophiles to Diene and Arene Complexes . . . 1004
Applications of Product Subclass 2 in Organic Synthesis . . . . . . . . . . . . . . . . . . . 1005
1.9.2.3
Method 3:
Addition of Carbon Nucleophiles and
Tandem Difunctionalizations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1005
1.9.3
Product Subclass 3: Osmium±Carbonyl Complexes . . . . . . . . . . . . . . . . . . . . . . 1007
1.9.4
Product Subclass 4: Osmate Esters and Related Species . . . . . . . . . . . . . . . . . 1008
Keyword Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1017
Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1055
Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1107
Science of Synthesis Original Edition Volume 1
© Georg Thieme Verlag KG
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Table of Contents
Science of Synthesis Original Edition Volume 1
© Georg Thieme Verlag KG