反応例 22.1 ラジカル反応

置 換

SO2Cl2Cl

peroxide

72%

M.S. Kharasch, H.C. Brown, J. Am. Chem. Soc., 61, 2142 (1939).

CH3CH2CH2CH3

CH3CH2CH2CH3Br2

Cl2

CH3CH2CHCH3

Cl

CH3CH2CHCH3

Br

CH3CH2CH2CH2–Cl

CH3CH2CH2CH2–Br

h!+

70% 30%

h!+

98% 2%

H. Sing, J.M. Tedder, J. Chem. Soc., 4737 (1964).

CH3CH2CH2ClCl2

25 ̊ C

CH3CH2CH2ClBr2

25 ˚C

CH3CH2CHCl

Br

CH3CH2CHCl

Cl

CH3CHCH2Cl

Br

CH3CHCH2Cl

Cl

CH2CH2CH2Cl

Br

CH2CH2CH2Cl

Clh!

+ +

12% 48% 30%

h!+ +

40% 60% trace

D.D. Tanner, M.W. Mosher, Can. J. Chem., 47, 715 (1969).

CH3CH2CH2CNCl2, 40 ̊ C

CH3CHCH2CN

Cl

ClCH2CH2CH2CNh!+

69% 31%

A. Bruylants, M. Tits, C. Dieu, R. Gauthier, Bull. Soc. Chim. Belg., 61, 266 (1952).

CH2CH3Cl2

PhNO2, 40 ˚C

CHCH3

Cl

CH2CH2Cl

+

81% 19%

G.A Russell, A. Ito, D.G. Hendry, J. Am. Chem. Soc., 85, 2976 (1963).

h!

CH2CH3Br2

CHCH3

Br

h!

~100%

G.A Russell, C. DeBoer, J. Am. Chem. Soc., 85, 3136 (1963).

CH2CH2CH2CH3Cl2

CCl4, 40 ̊ C

CH2CHCH2CH3

Cl

CH2CH2CHCH3

Cl

CHCH2CH2CH3

Cl

CH2CH2CH2CH2Cl

+

41%

29%

G.A Russell, A. Ito, D.G. Hendry, J. Am. Chem. Soc., 85, 2976 (1963).

h! +

+

23% 7%

CH3

O2N

Br2

CH2Br

O2N140~150 ̊ C, 2 h G.H. Coleman, G.E. Honeywell,

Org. Synth., Coll. Vol. 2, 443 (1943).59~60%

CH3

NO2

NBS, CCl4

(PhCO)2O2

CH2Br

NO2

A. Kalir,

Org. Synth., Coll. Vol. 5, 825 (1973).reflux, 6~8 h

CH3

Br2 !

H2O !

CaCO3

Br

CHO

Br

CHBr2

Br(tungsten lamp)h"

60~69%

G.H. Coleman, G.E. Honeywell,

Org. Synth., Coll. Vol. 2, 89 (1943).

CH3Cl2, PCl5 !

H2O

H2SO4

Cl

CHO

Cl

CHCl2

Cl(tungsten lamp)h"

54~60%

W.L. McEwen,

Org. Synth., Coll. Vol. 2, 133 (1943).

CH3

O2N

Br2

CH2Br

O2N140~150 ̊ C, 2 h G.H. Coleman, G.E. Honeywell,

Org. Synth., Coll. Vol. 2, 443 (1943).59~60%

CH3

NO2

NBS, CCl4

(PhCO2)2

CH2Br

NO2

A. Kalir,

Org. Synth., Coll. Vol. 5, 825 (1973).reflux, 6~8 h

CH3

CH3

2 Br2

CH2Br

CH2Brh! 125 ̊ C

48~53%

E. Stephenson,Org. Synth., Coll. Vol. 4, 984 (1963).

CH3

CH3

4 Br2

CHBr2

CHBr2

(CO2K)2

! H2O–EtOH

!

CHO

CHOh"

74~80% 74~80% (59~64% overall)

T.C. Bill, D.S. Tarbell, Org. Synth., Coll. Vol. 4, 807 (1963).

(tungsten lamp)

CH3

CH3

4 Br2

!

CHBr2

CHBr2

CHO

CHO

h"

95% H2SO4

70~110 ˚C

51~55% 81~84%

(tungsten lamp)

J.M. Snell , A. Weissberger, Org. Synth., Coll. Vol. 3, 788 (1955).

O

O

Br2O

O

Br

H2O

!

CO2H

CHO140 ˚C

65~68%

R.L. Shriner, F.J. Wolf, Org. Synth., Coll. Vol. 3, 737 (1955).

O

O

NBS, CCl4

!O

O

Br

h"

75~81%

J.A. Koten, R.J. Sauer,

Org. Synth., Coll. Vol. 5, 145 (1973).

S

CH3

NBS, benzene

!(PhCO2)2S

CH2Br

71~79%

E. Campaine, B.F. Tullar,Org. Synth., Coll. Vol. 4, 921 (1963).

BrNBS, CCl4

Ph (PhCO2)2

!

Ph Br

BrZn-Cu

PhDMF, 7~9 ˚C

T.F. Corbin, R.C. Hahn, H. Shechter, Org. Synth., Coll. Vol. 5, 328 (1973).

75~85%

NBS, CCl4

(PhCO2)2Brreflux, 2 h

58~64% F.L. Greenwood, M.D. Kellert, J. Sedlak,Org. Synth., Coll. Vol. 4, 108 (1963).

O O

HO O

NBS, CCl4

!

(PhCO2)2

AcOH

H2SO4

!

O O

Br

!

Et3N

O O

70%

+ CH2=O

M. Nakagawa, J. Saegusa, M. Tonozaka, M. Obi, M. Kiuchi, T. Ban,Org. Synth., Coll. Vol. 6, 462 (1988).

SO2

Cl2, CCl4

SO2

Cl

SO2

Cl

Cl

h! (250 W sunlamp)

15 min30~44%

Cl2, CCl4

h! (250 W sunlamp)

1 h 84~93%

T.C. Sedergran, D.C. Dittmer, Org. Synth., Coll. Vol. 7, 491 (1990).

CO2H

CO2H SO2Cl2, C6H6

(PhCO2)2 CO2H

CO2HCl Cl CO2H

200 ̊ C

G.M. Lampman, J.C. Aumiller, Org. Synth., Coll. Vol. 6, 271 (1988).

40~49%reflux, 22 h

OCH3

PCl5

Cl!

OCH2Cl

Cl

H. Gross, W. Bürger,

Org. Synth., Coll. Vol. 5, 221 (1973).

68~80%

OCH3

OCl2

Cl Cl OCCl3

Oh!

30~35 ˚C

82~91%

K. Kurita, Y. Iwakura,Org. Synth., Coll. Vol. 6, 715 (1988).

O2

OOH

70 ˚C1~2 days

44~57%

H.B. Knight, D. Swern,Org. Synth., Coll. Vol. 4, 895 (1963).

二重結合における置換

O

O

CO2H

OPh

O

O

OPh+

AgNO3, (NH4)2S2O3

H2O, 60 ~ 65 °C

61~69%

N. Jacobsen, Org. Synth., Coll. Vol. 6, 890 (1988).

+ PhSeSO2Ph1) h!, CCl4

2) H2O2, CH2Cl2 SO2Ph

H.-s. Lin, M.J. Coghlan, L.A. Paquette, Org. Synth., Coll. Vol. 8, 543 (1993).

付 加

CH3(CH2)5 H

O

H

CO2Et

H

EtO2C(PhCO2)2

C2HCl3, 85 ̊ CCH3(CH2)5 CO2Et

O

CO2Et

T.M. Patrick, Jr., F.B. Erickson, Org. Synth., Coll. Vol. 4, 430 (1963).

+

71~75%21~32 h

CO2Et

CN

CH3

CN

CO2Et

benzoyl peroxide

cyclohexane, !

M. Julia, M. Maumy, Org. Synth., Coll. Vol. 6, 586 (1988).

Me3SiH2NCH2CH2OH

t-BuOH

Me3SiCF2Br DBU

Me3Si

Br

CF2Br

Me3SiCF2

CF2Br2, CuCl

J. Conzalez, M.J. Foti, S. Elsheimer, Org. Synth., Coll. Vol. 9, 247 (1998).

NaBH4

!CCl4 CH2 CH(CH2)5CH3

(PhCO2)2CCl3CH2CH(CH2)5CH3+

75%

J. Am. Chem. Soc., 69, 1100 (1947)

ラジカルカップリング

HO2Fe(II), H2O2, H2SO4

CH2HO2 HO CH2 CH2 OH

E.L. Jenner, Org. Synth., Coll. Vol. 5, 1026 (1973).

酸 化

OH

N

O

Oaq. NaOCl, CH2Cl2, pH 9.5

catalysts: and KBr

0~15 ̊ C

82~84%

P.L. Anelli, F. Montanari, S. Quici, Org. Synth., Coll. Vol. 8,367 (1993).

OH O

IKOH

O

Pb(OAc)4, I2

benzene, 70~75 °C MeOH, ! 71~82%

Z. Majeski, Z. Hamersak, Org. Synth., Coll. Vol. 6,958 (1988).

SRN1 反応

O2N CH2Cl O2N CH2C(CH3)2

NO2

+ (CH3)2CNO2

–

N. Kornblum, Angew. Chem. Int. Ed. Engl., 14, 734 (1975).

Na+

92%

O2N C

CH3

CH3

NO2 O2N C

CH3

CH3

SPh+ PhS–

96%

N. Kornblum, et al., J. Am. Chem. Soc., 89, 5714 (1967).

DMF, 25 ̊ C, 20 min

O2N C

CH3

CH3

Cl NDMSO

O2N C

CH3

CH3

N Cl–

++

N. Kornblum, F.W. Stuchal, J. Am. Chem. Soc., 92, 1804 (1970).

rt, 10 h

90%

水素化スズを用いる水素化と関連反応

水素化

O OMe

OH

OMe

BzO

Bu3SnH/AIBNO OMe

OH

OMe

BzO

MeK. C. Nicolaou and H. J.

Mitchel, Angew. Chem., Int. Ed. Engl. 2001, 40, 1577

Br

OTBS

Me

OBn

Me

O

BnO

MeO

I

CHO

OTBS

Me

OBn

Me

O

BnO

MeO

CHO

Ph3SnH/AIBN

90%

C. M. Hayward, D. Yohannes and S. J. Danishefsky, J. Am. Chem. Soc., 115, 9345 (1993).

O

H

H

H O

OH HO

HO

O

O

H

H

H O

O HO

HO

O

O

H

H

H O

H HO

HO

OBu3SnH

1) NaH2) CS23) MeI

SMe

S

S. Iacono, J.R. Rasmussen, Organic Syntheses, Coll. Vol. 7, 139 (1990).

MeSCO

OSiPh2t-Bu

SBu3SnH

AIBN

OSiPh2t-Bu

86%

Theodorakis, A. et. al. Chem. Eur. J., 11, 7175 (2005).

O

OC(S)SMe

OMe

Me

MeSC(S)O

OMe

OMe

35%

Bu3SnH/AIBN

K. C. Nicolaou and H. J. Mitchel,

Angew. Chem., Int. Ed. Engl., 40, 1577 (2001).

転位

OAcO

AcO

BrAcO

OAc

Bu3SnH

OAcO

AcO

OAc

OAc

OAcO

AcOAcO

OAc

OAcO

AcO

OAc

OAc

AIBN, !

80%

B. Giese, K.S. Göninger, Org. Synth., Coll. Vol. 8, 583 (1993).

付加

OAcO

AcO

Br

AcO

OAc

CN

Bu3SnH OAcO

AcOAcO

OAc

CN

+Et2O, h!

B. Giese, J. Dupuis, M. Nix, Org. Synth., Coll. Vol. 8, 148 (1993).

53~56%

環化

Br

Bu3SnH

AIBN

CH3+

98% 2%

H

O

BrEtO

Bu3SnH

AIBN O

H

H

EtO

G. Stork, M. Kahn, J. Am. Chem. Soc., 107, 500 (1985).

SePh

O

Bu3SnH

AIBN

OH 82% (trans:cis = 62:38)

D.L. Boger, R.J. Mathvink, J. Org. Chem., 57, 1429 (1992).

benzene, 80 ̊ C

CH2(CO2Me)2

CO2Me

CO2Me

Me2C=CHCH2Br

CO2MeMeO2C

Bu3Sn

Me2C=CHCH2CH(CO2Me)2

CH2Br

MeO2C CO2Me

Bu3SnH, AIBN

80 °C

SiO2, CH2Cl2

NaOMe, MeOH, 0 ̊ C NaH, THF

0 ̊ C~ rtenolate alkylation

83~85% R. Mook, Jr., P.M. Sher, Organic Syntheses, Coll. Vol. 8, 381 (1993).

Me Me

OOI

Me

Me Me

O MeH

MeMe

O HMe

Me

85%, 4:1

Bu3SnH/AIBN

+

Shan, C.-K. Tetrahedron Lett., 31, 3745 (1990).

HH

I

Me

Bu3SnH/AIBN

benzene

80 °C

D.P. Curran, J. Am. Chem. Soc., 107, 1448 (1985).

HH HH

MeH

H

HH