反応例 10.1 カルボニル化合物のヒドリド 還元

反応例

10.1

アルデヒドとケトンの還元

NaBH4

H O

NaBH₄

EtOH OH

85%

O ^NaNO2

AcOH

O₂N O

1) NaBH₄ / MeOH

OH O₂N

–20 ˚C, 1 h 2) HCl / MeOH

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H. Griesser, et al., Org. Synth., Coll. Vol. 10, 577 (2004).

89~91% 73~74%

O

CO₂H ^{1) NaBH4} / 0.2 M NaOH OH

CO2H

O O

25 ˚C

2) H3O⁺ +

76% 20%

LiAlH₄

CH₃(CH₂)₅CHO CH₃(CH₂)₅CH₂OH 86%

LiAlH₄/Et₂O 1)

2) H₃O⁺

O

OEt

LiAlH₄/Et₂O reflux, 30 min

OH

OEt 1)

2) H₂O

10% H₂SO₄/H₂O

O 62~65%

W.F. Gannon, H.O. House,

Org. Synth., Coll. Vol. 5, 294 (1973).

O

CH₃

LiAlH4/Et2O OH

CH₃ 1)

2) H2O/Et2O 0 ˚C, 15 min

98%

Zn(Hg), HCl

Et2O, –15 ˚C CH₃ 68~75%

I. Elphimoff-Felkin, P. Sarda,

Org. Synth., Coll. Vol. 6, 769 (1988).

O OH

BF3·OBu2

CHO

OH OH

LiAlH₄/Et₂O reflux, 1 h 1)

2) Na₂SO₄/H₂O

80~95%

65~80%

J.P. Barnier, J. Champion, J.M. Conia, Org. Synth., Coll. Vol. 7, 129 (1990).

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O

t-Bu

t-Bu OH

H

H

t-Bu H

OH

H

LiAlH₄/Et₂O 1)

2) H₃O⁺ +

90% 10%

接触水素化

O H

OH

Ni or Pt or Pd/C H₂

エステルの還元

N

CO₂Et CH₃

LiAlH₄/Et₂O

1) reflux, 30 min 2) EtOAc 3) HCl/H₂O 4) NaOH

N

CH₂OH CH₃ 80~90%

R.B. Moffett, Org. Synth., Coll. Vol. 4, 834 (1963).

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OH CO₂Et CH₃H

LiAlH₄/Et₂O reflux, 3 h 1)

2) H₂O

OH

CH₂OH CH₃H

HBr AcOH

CH₃(CH₂)₄OK CH₃(CH₂)₄OH OH

CH₂Br CH₃H

O H CH₃ 68~73%

78~85% 69~81%

M.K. Ellis, B.T. Golding

Org. Synth., Coll. Vol. 7, 356 (1990).

カルボン酸の還元

CO₂H H Cl

R

LiAlH₄/Et₂O 1)

2) H₂O

CH₂OH H Cl

R R = Me, i-Pr, i-Bu, (S)-s-Bu 56~58%

KOH H₂O

O R H

68~70%

V.Schurig

Org. Synth., Coll. Vol. 8, 434 (1993).

H₂N CO₂H CH(CH₃)₂

H Method 1. LiAlH₄/THF

Method 2. BH₃·SMe₂

BF₃·OEt₂ H₂N CH₂OH CH(CH₃)₂ H

D.A. Dickman, A.I. Meyers, G.A. Smith, R.E. Gawley, Org. Synth., Coll. Vol. 7, 530 (1990).

HO₂C

CO₂Et HOCH₂

CO₂Et BH₃·THF

–10 ˚C~r.t.

A.S. Kende, P. Fludzinski, Org. Synth., Coll. Vol. 7, 221 (1990).

67%

酸塩化物の還元

Cl Cl

O

Cl

LiAlH₄/Et₂O 1)

2) H2SO4/H2O

Cl OH

Cl C.E. Sroog, H.M. Woodburn,

Org. Synth., Coll. Vol. 4, 271 (1963).

64~65%

アミドの還元

C₁₀H₂₁

NH O

CH₃ ^LiAlH4/Et2O C₁₀H₂₁

NH CH₃

81~95%

C.V. Wilson, J.F. Sterberg, Org. Synth., Coll. Vol. 4, 564 (1963).

C O

(CH₂)₆ C O

Cl H₂N(CH₂)₈NH₂

C O

(CH₂)₆ C O

NH HN (CH₂)₈

(CH₂)₈ (CH₂)₈

NH HN

+ ^benzene

25 ˚C

LiAlH₄/THF

51~52%

75%

C.H. Park, H.E. Simmons,

Org. Synth., Coll. Vol. 6, 382 (1988).

Cl

Cannizzaro 反応

O CHO

33% NaOH

H₂SO₄

O CO₂Na O CH₂OH

2 +

O CO₂H

60~63%

75~85%

20˚C, 2 h

W.C. Wilson,

Org. Synth., Coll. Vol. 1, 276 (1941).

CH₃

H O

+ H₂C O ^KOH/MeOH

CH₃

OH

90%

60~70 ˚C, 3 h

D. Davidson, M. Weiss, Org. Synth., Coll. Vol. 2, 590 (1943).

Tishchenko 反応

Ph H

O

2 ^{PhCH2ONa (cat.)}

Ph OCH₂Ph O

50~60 ˚C, 30 min

O. Kamm, W.F. Kamm,

Org. Synth., Coll. Vol. 1, 104 (1941).

90~93%