反応例 18.1 求電子性アルケンへの求核付加

シアン化物イオンの共役付加

H5C6 CH

C

C6H5

CN

KCN

MeOH, H2O

reflux, 1 h

H5C6 C6H5

NC CN 92-94%

J. A. McRae, R. A. B. Bannard, Org. Synth., Coll. Vol. 4, 393 (1963).

reflux, 5 h

G. B. Brown, Org. Synth., Coll. Vol. 3, 615 (1955).

MeCO2Et

NaCN

EtOH, H2O MeCO2Et

CN

reflux, 4 h

Ba(OH)2

H2O MeCO2H

CN

66-70%

reflux, 5 h

H5C6

COC6H5KCN

EtOH, AcOH MeCO2Et

CN

93-96%

C. F. H. Allen, R. K. Kimball, Org. Synth., Coll. Vol. 2, 498 (1943).

H5C6 CO2Et

CO2EtKCN

EtOH, H2O

65-75 °C, 18 h

HCl

reflux, 18 h

H5C6 CO2Et

NC

H5C6 CO2H

HO2C

67-70%

C. F. H. Allen, H. B. Johnson, Org. Synth., Coll. Vol. 4, 804 (1963).

アルコキシドの付加

F F

F

NaOEt

EtOHCl Cl

F F

F

OEtH

B. Englund, Org. Synth., Coll. Vol. 4, 184 (1954).

80~92%

Cl

O

CH(CH3)2NaOH

O

CH(CH3)2EtO

OEt

MeOH, –10 ˚C80~90%

C.C. Price, J.A. Pappalardo, Org. Synth., Coll. Vol. 4, 558 (1954).

硫黄求核種の付加

CO2Me H2Sreflux, 25 h

AcONa

CH2CH2CO2Me

CH2CH2CO2Me

S71-81%

R. F. Feldkamp, B. F. Tullar, Org. Synth., Coll. Vol. 4, 669 (1963).

アミンの反応

HC CHCO2HH5C6

NH2OH

EtOH, H2O

reflux, 9 h

HC CH2CO2HH5C6

NHOH

HC CH2CO2HH5C6

NH2

R. E. Steiger, Org. Synth., Coll. Vol. 3, 91 (1955).

34%

CO2Et

MeNH2

EtOH

rt, 6 d

N

CH2CH2CO2Et

CH2CH2CO2Et

Me

R. Mozingo, J. H. McCracken, Org. Synth., Coll. Vol. 3, 258 (1955).

83-86%

亜硝酸イオン（NO2–）の付加

CHONaNO2

H2O, THF, AcOH

0 °C, 3 h

NO2 CHO 89-91%

H. Griesser, R. Oehrlein, W. Schwab, E. Ehrler, V. Jaeger, Org. Synth., Coll. Vol. 10, 577 (2004).

ハロゲン化水素の付加（酸触媒求核付加）

CHOHCl

–10 ~ –15 °C

CHOCl

HNO3 CO2HCl

C. Moureu, R. Chaux, S. G. Powell, E. H. Huntress, E. B. Hershberg,

Org. Synth., Coll. Vol. 1, 166 (1941).

CHOHCl, EtOH

0 ̊ CCl OEt

OEt

34%

E.J. Witzemann, W.L. Evans, H. Hass, E.F. Schroeder, Org. Synth., Coll. Vol. 2, 137 (1943).

CHONH4Cl, EtOH

!

CHOEtO EtO OEt

OEt

+

7~8% 31~39%

C.G. Alberti, R. Sollazzo, Org. Synth., Coll. Vol. 3, 371 (1955).

CO2Me HBrrt, 1 h

CO2MeBr 80-84%

R. Mozingo, L. A. Patterson, Org. Synth., Coll. Vol. 3, 576 (1955).

Et2O

CHOHBr

CH2Cl2

HO OH TsOH

Br O

O

J. C. Stowell, D. R. Keith, B. T. King, Org. Synth., Coll. Vol. 7, 59 (1990).

65%

エノラートイオンの付加（Michael 反応）

CO2Et

CO2Et

EtO2CMe

NaOEt

EtOH

reflux, 1 h

NaO2CMe

NaO2C CO2Na

HCl

reflux, 8 h

HO2CMe

HO2C

Ac2O

steam bath, 1 h O

O

O

Me

J. Cason, Org. Synth., Coll. Vol. 4, 630 (1963).

H5C6

CO2Et

Me

CN

NC CONH2

NaOEt

EtOH

rt, 2 h

HCl

NH

H5C6 Me

CNNC

O O

90-92%

S. M. McElvain, D. H. Clemens, Org. Synth., Coll. Vol. 4, 662 (1963).

O

+MeO

CO2Me

CO2Me

LDA, THF, -78 °CO O

CO2Me

!"#$%

Organic Syntheses, Coll. Vol. 8, p.444 (1993); Vol. 65, p.98 (1987).

CO2Et

CO2Et

EtO2C

CO2Et

reflux, 1 h

NaOEt

EtO2C

CO2Et

CO2Et

EtO2C

93-94%

H. T. Clarke, T. F. Murray, Org. Synth., Coll. Vol. 1, 272 (1941).

O

O

NCCH2CO2EtNH4OH

EtOH

rt, 1 h

CH(CN)CO2Et

HO

CH(CN)CO2Et

OH

J. H. Wood, L. Cox, Org. Synth., Coll. Vol. 3, 286 (1955).

43-49%

MeCOMe

Me CO2Et

CO2Et

reflux, 2 h

NaOEt

EtOH

ONa

OMe

Me

EtO2C

reflux, 6 h

KOH

HCl

O

OMe

Me

67-85%

R. L. Shriner, H. R. Todd, T. F. Murray, Org. Synth., Coll. Vol. 1, 272 (1941).

Me

NO2CO2Me

PhCH2N+Me3 OH–

Me

MeCO2Me

NO2

Me

dioxane, H2O

steam bath, 1 h

R. B. Moffett, Org. Synth., Coll. Vol. 4, 652 (1963).

80-86%

PhCHCO2Et

CN

CNKOH

t-BuOH

PhCCH2CH2CN

CN

CO2Et

69~83%

E.C. Horning, A.F. Finelli, Org. Synth., Coll. Vol. 4, 776 (1963).

酸性条件での共役付加

O

O

NH

CO2–

O

DMSOOH

O

O

O

O

O

O

O

(57%)

+aq. HOAc

72~75 °C

(L-proline)

P. Buchschacher, A. Fürst, J. Gutzwiller Org. Synth., Coll. Vol. 7, 368 (19

90).

CO2Et

O

Me

OFeCl36H2O

rt, 6 h, reduced presssure

CO2Et

O

Me

O 91-93%J. Christoffers, Org. Synth., Coll. Vol. 10, 588 (2004).

Me

Me Me

CHO

Me

O

Me

Me Me

CHO

Me

OEt2NSiMe3

MeCN

reflux, 46 h

96%

H. Hagiwara, H. Ono, T. Hoshi, Org. Synth., 80, 195 (2003).

O Me OMe

200 °C, 12 h O

Me OMe

R. I. Longley, Jr., W. S. Emerson, A. J. Blardinelli, Org. Synth., Coll. Vol. 4, 311 (1963).

52-57%

O

O

O

reflux, 22 h

O

O

O42-54%

C. S. Rondestvedt, Jr., Org. Synth., Coll. Vol. 4, 766 (1963).

Cl

Cl

Ph Me

O

Me3Si

TiCl4

-40 °C, 40 min

Me

O

Ph

78-80%

H. Sakurai, A. Hosomi, J. Hayashi, Org. Synth., Coll. Vol. 7, 443 (1990).

有機金属およびヒドリドの反応

O

Me

Me

Me

BuMgCl, 30%MnO2, 3% CuCl

THF

0 °C, 2 hO

Me

Me

Me

Bu

94%

S. Marquais, M. Alami, G. Cahiez, Org. Synth., Coll. Vol. 9, 328 (1998).

Me

Me

Cl

O

Li

LiCuSPh

-15 ~ -20 °C

Me

Me

O

74%

P. A. Wender, A. W. White, F. E. McDonald, Org. Synth., Coll. Vol. 9, 350 (1998).

THF

D. C. Muchmore, Org. Synth., Coll. Vol. 6, 762 (1988).

Me

Me

Me

Me

MeH

O

LiCuMe2

Et2O

rt, 2 h

Me

LiO

ClPO(OEt)2

rt, 1 h

Me

(EtO)2P(O)OMe

Li, EtNH2

-15 °C, 15 min

Me

Me

45-51%

Me H

Me

Me

O

O

MeMgBr, CuBrSMe2 (cat),

Me3SiCl, HMPA, THF

Me

Me

OSiMe3

90-95%

Y. Horiguchi, E. Nakamura, I. Kuwajima, Org. Synth., Coll. Vol. 9, 564 (1998).

(CH2)5Me Cp2ZrHCL15-25 °C, 2 h

Cp2Zr (CH2)5Me

Cl

O

0 °C, 2 h

O

(CH2)5Me61%

R. C. Sun, M. Okabe, D. L. Coffen, J. Schwartz, Org. Synth., Coll. Vol. 9, 640 (1998).

O

PhB(OH)2

Rh(acac)(C2H4)2(R)-BINAP

H2O, dioxane100 °C, 3 h

O

Ph83%

T. Hayashi, M. Takahashi, Y. Takaya, M. Ogasawara, Org. Synth., Coll. Vol. 10, 609 (2004).

O

S

S

MeLi, CuI, DIBAL-H

HMPA, THF

-50 ~ 0 °C

O

S

S

92%

K. R. Dahnke, L. A. Pquette, Org. Synth., Coll. Vol. 9, 396 (1998).

Robinson環化反応

Me

O

Me2CuLi

Et2O

-78 to -20 °C, 1 h

Me

Me

O

O

SiMe3

Me

-20 ~ -30 °C

NH4Cl, NH4OH KOH

reflux, 4 h

MeMe

O

43-57%

R. K. Boeckman, Jr., D. M. Blum, Org. Synth., Coll. Vol. 6, 666 (1988).

Me

O

O

HO

Me AcOH

70 °C, 1~2 hO

Me O

Me

O

100%

Z. G. Hajps, D. R. Parrish, Org. Synth., Coll. Vol. 7, 363 (1990).

(S)-proline

DMF16 °C

Me

HO

O

O

H2SO4

DMF

95 °C

Me O

O 70-76%

MeO

O

O

Me KOH

MeOH

reflux, 3 h

O

O

Me

O

Me

NH

reflux, 30 min

Dean-Sark trapO

O

Me

63-65%

S. Ramachandran, M. S. Newman, Org. Synth., Coll. Vol. 5, 486 (1973).

C6H6

Me

N

Ph

MeH

MeO

Me

O

NH2

Ph

MeH

40 °C, 24 h

AcOH

O

Me

MeO

NaOMe

60 °C, 10 h

Me

O

44-48%

G. Revial, M. Pfau, Org. Synth., Coll. Vol. 9, 610 (1998).

toluene

エナミンの反応

N

O

Me

O

reflux, 4 h

H2O

reflux, 10~12 hO O

59-65%

R. L. Augustine, J. A. Caputo, Org. Synth., Coll. Vol. 5, 869 (1973).

dioxane

NMe

O

EtOH

reflux

NaOAc

reflux

NaOH

reflux

O

V. V. Kane, M. Jones, Jr., Org. Synth., Coll. Vol. 7, 473 (1990).

44-49%

Y. Chan, W, W, Epstein, Org. Synth., Coll. Vol. 6, 496 (1988).

Me CHO

Me

NH

reflux, 3.5 h

MeN

Me

94-95%

Me

O

rt, 4 h

O

Me

Me

N Me

HCl

rt, 14 h

Me

Me

O

71-85%

エノールシリルエーテルの反応

OSiMe3

Ph Me

Me

Ph

OTiCl4

CH2Cl2 Ph Ph

OMe MeO

72~78%

K. Narasaka, Org. Synth., Coll. Vol. 8, 210 (1993).

OSiMe3

Me

NO2

SnCl4

CH2Cl2 OO

M. Miyashita, T. Yanami, A. Yoshikoshi., Org. Synth., Coll. Vol. 7, 414 (1990).

61-70%