官能团转化全图解
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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
Ph
OH
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)