反応例
置
ラジカル反応
22.1
換
Cl
SO2Cl2
M.S. Kharasch, H.C. Brown,
J. Am. Chem. Soc., 61, 2142 (1939).
peroxide
72%
Cl
Cl2
CH3CH2CH2CH3
CH3CH2CHCH3 + CH3CH2CH2CH2–Cl
h!
70%
Br
Br2
CH3CH2CH2CH3
30%
CH3CH2CHCH3 + CH3CH2CH2CH2–Br
h!
98%
2%
H. Sing, J.M. Tedder, J. Chem. Soc., 4737 (1964).
CH3CH2CH2Cl
CH3CH2CH2Cl
Cl2
Cl
25 ˚C
Br2
Cl
Cl
+
+
CH3CH2CHCl
CH3CHCH2Cl
CH2CH2CH2Cl
h!
12%
48%
Br
30%
Br
Br
CH3CH2CHCl + CH3CHCH2Cl + CH2CH2CH2Cl
h!
25 ˚C
40%
60%
trace
D.D. Tanner, M.W. Mosher, Can. J. Chem., 47, 715 (1969).
CH3CH2CH2CN
Cl2 , 40 ˚C
h!
Cl
CH3CHCH2CN + ClCH2CH2CH2CN
69%
31%
A. Bruylants, M. Tits, C. Dieu, R. Gauthier, Bull. Soc. Chim. Belg., 61, 266 (1952).
CH2CH3
Cl2
h!
Cl
CHCH3
CH2CH2Cl
+
PhNO2, 40 ˚C
81%
19%
G.A Russell, A. Ito, D.G. Hendry, J. Am. Chem. Soc., 85, 2976 (1963).
Br
CH2CH3
CHCH3
Br2
h!
~100%
G.A Russell, C. DeBoer, J. Am. Chem. Soc., 85, 3136 (1963).
CH2CH2CH2CH3
Cl2
Cl
CHCH2CH2CH3
h!
CCl4, 40 ˚C
+
41%
Cl
Cl
CH2CHCH2CH3
CH2CH2CHCH3
CH2CH2CH2CH2Cl
+
+
23%
29%
7%
G.A Russell, A. Ito, D.G. Hendry, J. Am. Chem. Soc., 85, 2976 (1963).
CH3
140~150 ˚C, 2 h
O 2N
CH3
NO2
CH3
Br
CH2Br
Br2
O 2N
(PhCO)2O2
reflux, 6~8 h
CHBr2
!
Br
CHO
!
CaCO3
A. Kalir,
Org. Synth., Coll. Vol. 5, 825 (1973).
NO 2
h" (tungsten lamp)
H2O
59~60%
CH2Br
NBS, CCl4
Br2
G.H. Coleman, G.E. Honeywell,
Org. Synth., Coll. Vol. 2, 443 (1943).
Br
60~69%
G.H. Coleman, G.E. Honeywell,
Org. Synth., Coll. Vol. 2, 89 (1943).
CH3
Cl2, PCl5
CHCl2
!
h" (tungsten lamp)
Cl
Cl
H2SO4
H2 O
CH3
Cl
54~60%
CH2Br
Br2
140~150 ˚C, 2 h
O 2N
CH3
NO2
CH3
O 2N
(PhCO2)2
reflux, 6~8 h
CH3
59~60%
A. Kalir,
Org. Synth., Coll. Vol. 5, 825 (1973).
NO 2
CH2Br
2 Br2
h!
G.H. Coleman, G.E. Honeywell,
Org. Synth., Coll. Vol. 2, 443 (1943).
CH2Br
NBS, CCl4
CH3
W.L. McEwen,
Org. Synth., Coll. Vol. 2, 133 (1943).
CHO
125 ˚C
CH2Br
48~53%
CHBr 2
4 Br2
h" !
CH3 (tungsten lamp)
CHBr 2
74~80%
E. Stephenson,
Org. Synth., Coll. Vol. 4, 984 (1963).
CHO
(CO2 K)2
H 2O–EtOH
CHO
!
74~80% (59~64% overall)
T.C. Bill, D.S. Tarbell, Org. Synth., Coll. Vol. 4, 807 (1963).
CH3
CHBr2
95% H2SO4
4 Br2
h" !
(tungsten lamp)
CH3
CHO
70~110 ˚C
CHBr2
51~55%
CHO
81~84%
J.M. Snell, A. Weissberger, Org. Synth., Coll. Vol. 3, 788 (1955).
O
O
Br2
O
O
140 ˚C
CO2H
H2O
!
CHO
Br
65~68%
R.L. Shriner, F.J. Wolf, Org. Synth., Coll. Vol. 3, 737 (1955).
O
O
NBS, CCl4
O
h"
J.A. Koten, R.J. Sauer,
Org. Synth., Coll. Vol. 5, 145 (1973).
O
!
75~81% Br
CH3
CH2Br
NBS, benzene
!
(PhCO2)2
S
71~79%
Br
NBS, CCl4
Br
Ph
S
E. Campaine, B.F. Tullar,
Org. Synth., Coll. Vol. 4, 921 (1963).
Zn-Cu
Ph
(PhCO2)2
Br
DMF, 7~9 ˚C
!
Ph
75~85%
T.F. Corbin, R.C. Hahn, H. Shechter, Org. Synth., Coll. Vol. 5, 328 (1973).
NBS, CCl4
(PhCO2)2
reflux, 2 h
+ CH2=O
HO
O
NBS, CCl4
O
O
(PhCO2)2
!
58~64%
Br
F.L. Greenwood, M.D. Kellert, J. Sedlak,
Org. Synth., Coll. Vol. 4, 108 (1963).
H 2SO4
AcOH
!
Br
Et 3N
O
O
!
O
O
70%
M. Nakagawa, J. Saegusa, M. Tonozaka, M. Obi, M. Kiuchi, T. Ban,
Org. Synth., Coll. Vol. 6, 462 (1988).
SO 2
Cl
Cl
Cl2, CCl4
h! (250 W sunlamp)
15 min
Cl2, CCl4
Cl
h! (250 W sunlamp)
SO2
SO 2
1h
30~44%
84~93%
T.C. Sedergran, D.C. Dittmer, Org. Synth., Coll. Vol. 7, 491 (1990).
CO 2H
CO 2H
SO2Cl2, C6H 6
(PhCO2)2
CO2H
Cl
200 ˚C
Cl
CO2H
CO 2H
40~49%
reflux, 22 h
G.M. Lampman, J.C. Aumiller, Org. Synth., Coll. Vol. 6, 271 (1988).
OCH3
OCH2Cl
PCl5
!
Cl
H. Gross, W. Bürger,
Org. Synth., Coll. Vol. 5, 221 (1973).
Cl
68~80%
O
Cl
O
Cl2 h!
OCH3
Cl
30~35 ˚C
OCCl3
K. Kurita, Y. Iwakura,
Org. Synth., Coll. Vol. 6, 715 (1988).
82~91%
OOH
O2
H.B. Knight, D. Swern,
Org. Synth., Coll. Vol. 4, 895 (1963).
70 ˚C
1~2 days
44~57%
二重結合における置換
O
O
CO 2H
+
OPh
O
AgNO3, (NH 4)2S2O3
OPh
H2O, 60 ~ 65 °C
O
61~69%
N. Jacobsen, Org. Synth., Coll. Vol. 6, 890 (1988).
+
1) h!, CCl4
PhSeSO2Ph
2) H2O2, CH2Cl2
SO2Ph
H.-s. Lin, M.J. Coghlan, L.A. Paquette, Org. Synth., Coll. Vol. 8, 543 (1993).
付
加
EtO2C
O
CO 2Et
+
CH3(CH2)5
H
H
H
O
(PhCO2)2
CH3(CH2) 5
C2HCl3, 85 ˚C
21~32 h
71~75%
CO2Et
CO 2Et
T.M. Patrick, Jr., F.B. Erickson, Org. Synth., Coll. Vol. 4, 430 (1963).
CO2Et
CH3
benzoyl peroxide
CO 2Et
cyclohexane, !
CN
CN
M. Julia, M. Maumy, Org. Synth., Coll. Vol. 6, 586 (1988).
Br
CF2Br2, CuCl
Me3Si
NaBH4
H2NCH 2CH 2OH
t-BuOH
Me 3Si
CF2Br
DBU
Me3Si
CCl4 + CH2 CH(CH2) 5CH3
(PhCO2 )2
!
CF2Br
Me3Si
J. Conzalez, M.J. Foti, S. Elsheimer,
Org. Synth., Coll. Vol. 9, 247 (1998).
CF2
CCl3CH2CH(CH2)5CH3
75%
J. Am. Chem. Soc., 69, 1100 (1947)
ラ ジ カルカップリング
2 HO
Fe(II), H2O2, H2SO4
2 HO
CH2
HO
CH2 CH2
OH
E.L. Jenner, Org. Synth., Coll. Vol. 5, 1026 (1973).
酸
化
aq. NaOCl, CH2Cl2, pH 9.5
O
OH
catalysts:
and KBr
N
O
82~84%
0~15 ˚C
P.L. Anelli, F. Montanari, S. Quici, Org. Synth., Coll. Vol. 8,367 (1993).
OH
O
I
O
KOH
Pb(OAc)4, I 2
MeOH, !
benzene, 70~75 °C
71~82%
Z. Majeski, Z. Hamersak, Org. Synth., Coll. Vol. 6,958 (1988).
SRN1 反応
–
O 2N
CH2Cl + (CH3)2CNO2
+
Na
O 2N
92%
CH2C(CH3) 2
NO2
N. Kornblum, Angew. Chem. Int. Ed. Engl., 14, 734 (1975).
CH3
O 2N
–
C NO2 + PhS
CH3
CH3
DMF, 25 ˚C, 20 min
O 2N
C SPh
CH3
96%
N. Kornblum, et al., J. Am. Chem. Soc., 89, 5714 (1967).
CH3
C Cl +
O 2N
N
DMSO
O2N
rt, 10 h
CH3
CH3
+
C N
Cl–
CH3
90%
N. Kornblum, F.W. Stuchal, J. Am. Chem. Soc., 92, 1804 (1970).
水素化スズを用いる水素化と関連反応
水素化
O
Br
OMe
Bu 3SnH/AIBN
BzO
OH
Me
O
BzO
OMe
Me
BnO
Ph3SnH/AIBN
Me
OBn
MeO
I
K. C. Nicolaou and H. J.
Mitchel, Angew. Chem., Int.
Ed. Engl. 2001, 40, 1577
OH
OMe
BnO
OMe
O
Me
Me
OBn
MeO
O
OTBS
CHO
90%
OTBS
CHO
C. M. Hayward, D. Yohannes and S. J. Danishefsky, J. Am. Chem. Soc., 115, 9345 (1993).
O
H
O
O
OH H
H
H
O
H
1) NaH
2) CS2
3) MeI
S
O
SMe
H
O
O
H
O
H
O
O
H
H
O
Bu3SnH
O
H
O
H
O
H
H
H
H
O
O
S. Iacono, J.R. Rasmussen, Organic Syntheses, Coll. Vol. 7, 139 (1990).
OSiPh2t-Bu
S
MeSCO
OSiPh2t-Bu
Bu3SnH
AIBN
86%
Theodorakis, A. et. al.
Chem. Eur. J., 11, 7175 (2005).
Me
O
Bu3SnH/AIBN
Me
O
K. C. Nicolaou and H. J. Mitchel,
Angew. Chem., Int. Ed. Engl.,
40, 1577 (2001).
OC(S)SMe
MeSC(S)O
35%
OMe
OMe
転位
OAc
AcO
AcO
OAc
Bu3SnH
O
AcO
O
AcO
AcO
AIBN, !
OAc
AcO
Br
O
AcO
AcO
OAc
OAc
O
AcO
AcO
80%
OAc
B. Giese, K.S. Göninger,
Org. Synth., Coll. Vol. 8, 583 (1993).
付加
OAc
OAc
O
AcO
AcO
Bu3SnH
+
CN
Et2O, h!
AcO
Br
O
AcO
AcO
AcO
CN
53~56%
B. Giese, J. Dupuis, M. Nix, Org. Synth., Coll. Vol. 8, 148 (1993).
環化
Br
Bu3SnH
CH3
AIBN
98%
Bu3 SnH
H
AIBN
O
EtO
Br
H
O
+
2%
H
EtO
G. Stork, M. Kahn, J. Am. Chem. Soc., 107, 500 (1985).
SePh
Bu3SnH
AIBN
benzene, 80 ˚C
O
H
O
82% (trans :cis = 62:38)
D.L. Boger, R.J. Mathvink, J. Org. Chem., 57, 1429 (1992).
Me2 C=CHCH2Br
CH2(CO 2Me) 2
Me2C=CHCH2CH(CO2Me) 2
NaOMe, MeOH, 0 ˚C
enolate alkylation
CH 2Br
NaH, THF
0 ˚C~ rt
MeO2C CO2Me
MeO2C CO 2Me
CO2Me
Bu3SnH, AIBN
CO2Me
80 °C
SiO2, CH 2Cl2
Bu3Sn
83~85%
R. Mook, Jr., P.M. Sher, Organic Syntheses, Coll. Vol. 8, 381 (1993).
O
O
I
Bu3SnH/AIBN
Me Me
Me Me
O H
O Me
Me
H
+
Me Me
85%, 4:1
Me Me
Shan, C.-K. Tetrahedron Lett., 31, 3745 (1990).
H
I
Me
Bu3SnH/AIBN
benzene
80 °C
H
H
H
H
H
H
H Me
D.P. Curran, J. Am. Chem. Soc., 107, 1448 (1985).
H
H