官能团转化全图解

i 5-7-g f e d c b a e d c b a i h g f e

d c b

a h g f e d c

b a h g f e d

c b a 6-4-3-1-2-i h g f e

d c b a C=C -C(O)-CH 3

CH-CH CH-CX Functional Group Interconversion

C=C

C C C=C

C C RCH 2-SO 2Ph RC CH

C C C-NH 2; C-NO 2C-OH

C(OR)2

; C(SR)2C=C-OR; C=C-SR C C C N

C=N-OH, C=N-H C=S

C=O C=O C-C(O)Z C=C C=O C-OH C-X C-N C-H C-N C=O C---OH C-OC(O)R C-X C-OCH 2OR C-NH 2

C-OR C-H C-OH C=C C-H C(O)OR C-(OR)2C-OH C-OR

C-CHO C-CO 2H C-CN C=C C=O C-S C-X C-OH C-H C=C j C(O)X

h

C N

j k

C-H

C-Br 8-C-X

i C-OH

C-OH C(O)Z

d c b a

e d c b a

f C-NH 2C-H

j CX-CY

C C

X

C=O h g f i

C CH RCH(CO 2H)-CH 3-C(O)-CH 3

O

O

O

X

CRR'=CHX

j

C O C-NH 2C-CN

9-C-CH 3

C-X

a e C=O

1-a

dry pyridine: from CaH 2 and distilled

triflate

mesylate tosylate S O O O RCH 2CF 3

S O

O O RCH 2CH 3

CH 3

CH 3

CH 3

OH (2). for 3' alcohol:

LiAlH 4

(1). for 1', 2' alcohol:

1-i h g f e d c b a C-CHO C-CO 2H

C-CN C=C C=O C-S C-NH 2C-X C-OH C-H

CH 3

CH

3

CH 3

H n -Bu 3SnH C S O Ph

Cl RCH 2-H

CH 3

S

O

O O RCH 2CH 3

S O

O

Cl RCH 2OH

purification textbook

~ $ 30 / Kg toluenesulfonyl chloride (s)methanesulfonyy chloride (l)~ $ 30 / Kg j

C(O)X

Ph 2SiHCl / InCl 3Ph Ph

H

Ph

Ph

JOC, 2001, 66, 7741.

ii. Ph 2SiHCl / InCl 3

i. p -TsCl // LiAlH 4

i. ClC(S)OPh // n -Bu 3SnH Cl 22

via:

a unique Lewis acid catalyst, acceleratedeoxgyenation

InCl 3

indium trichloride

ii. Et 3SiH / Lewis acid

J. Org. Chem. 2000, 65, 6179

JOC, 2000, 65, 6179.

2rt, 3 hr

1-b Bu 3SnH: (l), easy to remove Ph 3SnH: (s), hard to remove Me 3SnH: too volatile, toxic

unstable in acid, form H 2 gas; stable in weak base

NaBH 3CN: stable at pH 5-6

hygroscopic, dried self, suggest: buy small amount each time

(Grignard reagent)

H 2O

Mg / Et 2O JOC, 1969, 34, 3923.

H

Br

Na / NH 3; Li / NH 3; Na / EtOH

Zn; Fe; Sn; Mg

(3). metal reduction (2). hydride reduction

(1). free radical reduction

JACS, 1972, 94, 8905.n -Bu 3SnH H

Br

NaBH 4 / InCl 3 / CH 3CN

radical reagent

n -Bu 3SnH / AlBN JA CS, 2002, 124, 906.

i iii NaBH 3CN

i LiAlH 4

i ii ii NaBH 4

ii THL, 1969, 3095.

JOC, 1976, 41, 3064.

iv LiBHEt 3 (super hydride)