反応例 18.1 求電子性アルケン へ の求核付加

反応例 

18.1

シアン化物イオンの共役付加

H

C

C H C

C

H

CN

KCN MeOH, H

O

reflux, 1 h

H

C

C

H

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).

Me CO

Et NaCN

EtOH, H

O Me CO

Et CN

reflux, 4 h Ba(OH)

H

O Me CO

H CN

66-70%

reflux, 5 h H

C

COC

H

KCN

EtOH, AcOH Me CO

Et CN

93-96%

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

H

C

CO

Et

CO

Et KCN EtOH, H

O 65-75 °C, 18 h

HCl reflux, 18 h H

C

CO

Et NC

H

C

CO

H HO

C

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

Cl

Cl

F F

F OEt H

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

80~92%

Cl

O

CH(CH

)

O

CH(CH

)

EtO

OEt

MeOH, –10 ˚C

80~90%

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

硫黄求核種の付加

CO

Me H

S

reflux, 25 h AcONa

CH

CH

CO

Me CH

CH

CO

Me

S 71-81%

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

アミンの反応

H C CHCO

H H

C

NH

OH EtOH, H

O

reflux, 9 h

H C CH

CO

H H

C

NHOH

H C CH

CO

H H

C

NH

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

34%

CO

Et

MeNH

EtOH rt, 6 d

N

CH

CH

CO

Et CH

CH

CO

Et Me

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

83-86%

亜硝酸イオン（

NO

–）の付加

CHO NaNO

H

O, THF, AcOH

0 °C, 3 h

NO

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）

CHO

–10 ~ –15 °C

Cl CHO

HNO₃

CO

H Cl

C. Moureu, R. Chaux, S. G. Powell, E. H. Huntress, E. B. Hershberg, Org. Synth., Coll. Vol. 1, 166 (1941).

CHO

0 ˚C

Cl OEt

OEt

34%

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

CHO

!

EtO CHO EtO OEt

OEt +

7~8% 31~39%

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

CO

Me HBr

rt, 1 h Br CO

Me 80-84%

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

Et

O

CHO HBr CH

Cl

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

CO

Et CO

Et

EtO

C Me NaOEt reflux, 1 h EtOH

NaO

C Me NaO

C CO

Na

HCl reflux, 8 h

HO

C Me HO

C

Ac

O

steam bath, 1 h O O

O

Me

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

H

C

CO

Et Me

CN

NC CONH

NaOEt EtOH

rt, 2 h

HCl

N H H

C

Me NC CN

O O

90-92%

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

O

+ MeO

CO₂Me CO₂Me

LDA, THF, -78 °C O O

CO₂Me

!"#$%

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

CO

Et CO

Et

EtO

C

CO

Et

reflux, 1 h NaOEt

EtO

C

CO

Et CO

Et EtO

C

93-94%

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

O

O

NCCH

CO

Et NH

OH EtOH

rt, 1 h

CH(CN)CO

Et HO

CH(CN)CO

Et OH

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

43-49%

Me COMe

Me CO

Et

CO

Et

reflux, 2 h NaOEt

EtOH

ONa

Me O Me EtO

C

reflux, 6 h KOH

HCl

O

Me O Me

67-85%

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

Me

NO

CO

Me

PhCH₂N⁺Me₃ OH^–

Me

Me CO

Me NO

Me

dioxane, H₂O

steam bath, 1 h

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

80-86%

PhCHCO

Et CN

CN

t-BuOH

PhCCH

CH

CN CN

CO

Et 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

DMSO

OH

O

O

O

O

O

O

O

(57%)

+ ^{aq. HOAc}

72~75 °C

(

-proline)

P. Buchschacher, A. Fürst, J. Gutzwiller 

Org. Synth

CO

Et O

Me

O FeCl

6H

O rt, 6 h, reduced presssure

CO

Et 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 Et

NSiMe

O

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

42-54% O C. S. Rondestvedt, Jr., Org. Synth., Coll. Vol. 4, 766 (1963).

Cl Cl

Ph Me

O

Me

Si

TiCl

-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%MnO

, 3% CuCl THF

0 °C, 2 h O

Me Me Me

Bu

94%

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

Me Me

Cl O

Li Li CuSPh

-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 H Me

O

LiCuMe

Et

O rt, 2 h

Me

LiO

ClPO(OEt)

rt, 1 h

Me

(EtO)

P(O)O

Me

Li, EtNH

-15 °C, 15 min

Me

Me

45-51%

Me H Me

Me O

O

MeMgBr, CuBrSMe

(cat), Me

SiCl, HMPA, THF

Me Me

OSiMe

90-95%

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

(CH

)

Me Cp

ZrHCL

15-25 °C, 2 h Cp

Zr

(CH

)

Me Cl

O

0 °C, 2 h

O

(CH

)

Me 61%

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

O

PhB(OH)

Rh(acac)(C

H

)

(R)-BINAP H

O, dioxane

100 °C, 3 h

O

Ph 83%

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

Me

O

Me

CuLi Et

O -78 to -20 °C, 1 h

Me Me

O

O SiMe

Me

-20 ~ -30 °C

NH

Cl, NH

OH KOH reflux, 4 h

Me Me

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 h

O

Me O

Me O

100%

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

(S)-proline DMF 16 °C

Me

HO O

O

H

SO

DMF 95 °C

Me O

O 70-76%

Me O

O

O

Me KOH

reflux, 3 h MeOH

O

O Me

O Me

NH

reflux, 30 min Dean-Sark trap O

O

Me

63-65%

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

C

H

Me

N Ph

Me H O Me

Me

O

NH

Ph

Me H 40 °C, 24 h

AcOH

O Me

O Me

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

H

O reflux, 10~12 h

O O

59-65%

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

dioxane

N Me

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

Me N

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

OSiMe

Ph Me

Me

Ph

O

CH₂Cl₂

Ph Ph

Me Me O O

72~78%

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

OSiMe

Me NO

SnCl

CH

Cl

O O

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

61-70%