1,3-[Bis(diphenylphosphino)propane]nickel(II) chloride
Catalog #: 416
Alternative name: NiCl2(dppp)
CAS Numbers: [15629-92-2]
Ph
Ph
P
Cl
Ni
Cl
P
Ph
Ph
C27H26Cl2NiP2
Mol. Wt.: 542.04
NiCl2(dppp) is an air stable square planar, dark red or purple complex. NiCl2(dppp) is a useful catalyst in
preparation of C-C bonds via coupling with Grignard reagents.
R'
Facile and Selective Deallylation of Ethers,
Amines, and Amides
R
O
R = 4-MeO-C6H4, PhCH2CH2,
(L)-menthyl, cholesteryl,
1-adamantyl, 6-benzyloxymethyl-α(β)-furanose
acetal, -CH2CH=CHCH2OBn,
(1S,4R,5S,6R)-4,5,6-(OBn)3-2cyclohexenyl, -(CH2)3OR'
R' = t-BuMe2Si, 4-MeO-C6H4-,
Bn, prenyl, MOM, THP
acetyl, pivaloyl, benzoyl
NiCl2(dppp)
DIBAL, solvent,
0-23 °C
R
NiCl2(dppp)
R'
N
R
H
DIBAL, toluene,
0-23 °C
amines: 66-91% yield (13 examples)
R = CH2CH2Ph, Bn, H
N-heteroaromatic: 71-86% yield (5 examples)
R' = Bn, Me, CH2CH=C(Me)2,
sulfonamides: 81-95% yield (4 examples)
allyl, H, p-tolSO2, C(O)R"
amides: 51-92% yield (8 examples)
R" = Me, Ph, Bn, 4-MeO-C6H4
R/R' = O-Bn-2-prolinol, indole, 1,2,3,4tetrahydroisoquinoline, tetrahydrocarbazole, 3,5-(Me)2-pyrazole,
carbazole
R
In combination with diisobutylaluminum
(DIBAL), NiCl2(dppp) catalyzes the selective
allylic deprotection of ethers, amines, and
amides.1, 2 Allyl groups can be cleaved in the
presence of O-benzyl groups. DIBAL can be
substituted with AlEt3 or NaBH4 in the
deallylation of ethers with ester functionality.
Allylic deprotection is only observed with
nonsubstituted allylic substituents. A general deN-allylation of basic, neutral, and acidic
nitrogens by NiCl2(dppp)/DIBAL has been
reported. Facile and chemoselective deprotection
was accomplished with secondary and tertiary
N
amines, primary and secondary amides, Nheteroaromatic compounds, sulfonamides. De-Nallylation of carbamates was possible, but not
consistent.
Regioselective and Stereospecific
Hydroboronylation of Thioalkynes
OH
71-97% yield
21 examples
Hydroboration of 1-(alkylthio)-1-alkynes with
catecholborane in the presence of NiCl2(dppp)
proceeds regio- and stereospecifically with high
yields. Boronation occurs preferentially at the β
position relative to the sulfur. Nickel catalysts
with 1,2-bis(diphenyl-phosphino)ethane (dppe)
can also be used with high yields and slightly
higher regio- and stereoselectivities (β/α =
>99:1).3
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RS
R'
O
S
O
R'
R
C6H4O2B
NiCl2(dppp)
benzene
a: R = Et, R' = Me
b: R = Ph, R' = H
NiCl2(dppp)-catalyzed coupling of 3 with
RMgBr selectively displaces the sulfoximine
group to form an α-magnesio alkenyl derivative
4.5
+
BH
H
α
RS
93-97% yields; β/α: 98:2
R'
H
BO2C6H4
β
Nickel-catalyzed Cross-Coupling with Grignard
Reagents
Numerous reports of C-C bond formations have
published. NiCl2(dppp) has been used to couple
Grignard reagents with various partners that
include aryl halides (Kumada reaction),6, 7 aryl
triflates,8 vinyl halides,9-11 aryl fluorides,12
N,N-dialkylheteroaromatic
ethers,13
14, 15
carbamates,
arenesulfonates,16 cyclic and
acyclic
dienyl
phosphates,17
oxabicyclic
18
compounds,
alkylenyl
sulfoximines,5
thioimidates,19 and vinyl sulfides20 with varying
degrees of success. Other sections will highlight
unique organic transformations with Grignard
reagents.
Nickel-catalyzed Cross-Coupling of
Dialkylpyrazines with Zinc Reagents
NiCl2(dppp) has been used to couple R2Zn with
heteroaryl chlorides to prepare trialkylpyrazines.4
R1
N
R1
N
Cl
R1 = Me, iPr,
iBu, sBu
N
R1
N
R
R2Zn
NiCl2(dppp)
R1
R = Me, Et,
iso-pentyl
70-93% yield
(5 examples)
Nickel-catalyzed Cross-Coupling of Alkenyl
Sulfoximines with Zn/Mg Reagents
Geminal Dimethylation of Allylic Dithioacetals
The asymmetric synthesis of alkyl- and arylsubstituted exocyclic alkenes is accomplished by
NiCl2(dppp)-catalyzed coupling with alkenyl
sulfoximines in high diastereoselectivities.
Enantiomerically
pure
MeN(H)-SO-Ph
(>98%ee) is liberated during the reaction.
Coupling will not occur without the presence of
salts (MgBr2, ZnCl2, LiBr). Interestingly,
addition of PhMgBr to 1 quantitatively metalates
to form an α-metallo-alkenyl sulfoximine E/Z-3.
A geminal dimethyl group is introduced
regioselectively and in excellent yields from the
reaction of allylic dithioacetals and MeMgI in
the presence of NiCl2(dppp) and NiCl2(dppe).21,
22
Several geminal dimethylation methods exist,
but are not applicable to α,β-unsaturated
carbonyl compounds because of poor
regioselectivity. The use of bisphosphine ligands
eliminates the formation of butadienes (6).
Dithioacetal generated from an allylic ketone (R’
= Me) produce a tert-butyl group under these
conditions.22
O
Ph
MeN
R
S
H
H
S
R2Zn
R
salts
NiCl2(dppp)
S
R'
NiCl2(dppp) or
NiCl2(dppe)
MeMgI, THF
reflux, 24 h
R = Ph, 4-MeC6H4, 3-MeOC6H4,
2-Naphthyl, 2-MeOC6H4
R' = H, Me
R'O
R'O
R'O
2
1
R' = SiMe2t-Bu R = Ph, m-C6H4CH2OR'
70-89% yield
R" = SiPh2t-Bu
-(CH2)4OR"
99:1 diastereoselectivity
R'O
Me
R
Me
R'
+
R
5
6
R = H: 90-98% yield (6 examples)
5:6 ratio: 96:4 to 100:0
R' = Me: 81% yield (1 example)
5:6 ratio: 100:0
Nickel-Catalyzed Cross Coupling of Cyclic
Sulfamates
O
1
PhMgBr
Ph S
MeN
R
MgBr
MgBr
R2Zn
salts
NiCl2(dppp)
3
E/Z (1:1)
4
E/Z (1:1)
Benzene-fused cyclic sulfamates called 1,2,3oxathiazinane-2,2-dioxides, are prepared from
ortho-substituted phenolic sulfamates through
selective C-H amination or olefin aziridination
with
Rh2(OAc)2/PhI(OAc)2/MgO.
These
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R'
heterocycles can undergo nickel-catalyzed cross
coupling with aryl- and alkyl-Grignards to form
unique benzylic amines.23
O
O
S
3.
4.
5.
O
R3
N
R
R3
HN
6.
RMgX
R1
R1
NiCl2(dppp),
C6H6/Et2O,
55 °C, 6h
7.
8.
R2
R2
9.
10.
11.
R = Me, Cy, TMSCH2-, R3 = Me, n-Pr, i-Bu,
72-95% yield
i-Bu, n-Bu, Ph,
4-MeOC6H4CH2(10 examples)
PhC(Me)2CH2R1/R2 = -(CH2)3-,
-CH2CH(OMe)CH2-,
R1 = Me, ring system
R2 = H, ring system
-CH2CH(OSi(Me)2tBu)CH2-
12.
13.
Preparation of Highly Conductive,
Regioregular Polymers
14.
Poly(3-alkylthiophene)s (P3ATs), 10, are
conjugated polymers that have been highly
investigated
due
to
good
solubility,
processability, environmental stability, and
spectroscopic and electronic properties. P3ATs
have been used in rechargeable battery
electrodes, sensors, light-emitting diodes, field
effect transistors, and non-linear optical
materials. NiCl2(dppp) is the preferred catalyst in
the preparation of regiocontrolled, head-to-toe
(HT) P3ATs.24 The initial formation of 3alkylthiophenes
(8)
was
prepared
by
NiCl2(dppp)-catalyzed coupling of 7 with
Grignard reagents. After Grignard metathesis of
9 with MeMgBr, polymerization occurs with HT
regioregularities >99%.25-28 This transformation
has been successfully applied to 3-ester and 3alkyloxy thiophenes with high regioregularities
(>98%).29, 30
Br
Br2
RMgBr
S
7
NiCl2(dppp)
Et2O, 35 °C
61-80% yields
(R = alkyls only)
Br
CHCl3
S
Br
S
8
9
R
R
R
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
US Sales
R
R
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1. MeMgBr/THF
2. NiCl2(dppp)
*
*
R = alkyls, alkoxys,
esters,
S
S
10
S
n
HT regioregularity
Mw range
91 to >99%
12,000 up to 50,000
PDIs = 1.1 to 1.78
References:
1.
2.
Taniguchi, T. and Ogasawara, K., Angew. Chem. Int.
Ed., 1998, 37(8), 1136.
Taniguchi, T. and Ogasawara, K., Tetrahedron Lett.,
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