化学官能团相互转换大全(part1)

1

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 )-C H 3C H -C H C H -C X Functiona l G roup Interconversion

C =C

C C C =C

C C R C H 2-SO 2Ph R C C H C C C -N H 2; C -N O 2C -O H

C (O R )2; C (SR )2C =C -O R ; C =C -SR C C C N

C =N -O H , C =N -H C =S

C =O C =O C -C (O )Z C =C

C =O C -O H C -X C -N C -H C -N C =O C ---O H C -O C (O )R C -X C -O C H 2O R C -N H 2

C -O R C -H C -O H C =C C -H C (O )O R C -(O R )2C -O H

C -O R

C -C H O C -C O 2H C -C N C =C C =O C -S C -X C -O H C -H C =C

j C (O )X

h

C N

j k

C -H

C -B r

8-C -X

i C -O H

C -O H C (O )Z d c b a e d c b a f

C -N H 2C -H

j

C X -C Y

C

C

X C =O h g

f i

C C H R C H (C O 2H )-C H 3-C(O )-C H 3

O

O O

X

C R R '=C H X

j

C O C -N

H 2C -C N

9-C -C H 3

C -X

a e C =O

2

1-a

dry pyridine: from C aH 2 and distilled

triflate

m esylate tosylate S O

O

O

R C H 2C F 3

S

O

O O

R C H 2C H 3C H 3

C H 3

C H 3

O H (2). for 3' alcohol:

LiA lH 4

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

1-i h

g f e d

c b a C -C H O C -C O 2H

C -C N C =C C =O C -S

C -N H 2C -X C -O H C -H C H 3

C H 3

C H 3

H n -B u 3SnH

S O

Ph

C l

R C H 2-H

C H 3

S O

O O

R C H 2C H 3

S O

O

C l

R C H 2O H

purification textbook

~ $ 30 / K g

toluenesulfonyl chloride (s)m ethanesulfonyy chloride (l)~ $ 30 / K g j

C (O )X

Ph 2SiH C l / InC l 3

Ph

Ph

H

Ph O H

Ph

JO C , 2001, 66, 7741.

ii. P h 2SiH C l / InC l 3

i. p -TsC l // LiA lH 4

i. C lC (S)O Ph // n -B u 3SnH

C l 2l

2

via:

a unique Lew is acid catalyst, acceleratedeoxgyenation

InC l 3

indium trichloride

ii. Et 3SiH / Lew is acid

J. O rg. C hem. 2000, 65, 6179

JO C , 2000, 65, 6179.

2rt, 3 hr

3

1-b

B u 3SnH : (l), easy to rem ove Ph 3SnH : (s), hard to rem ove M e 3SnH : too volatile, toxic

unstable in acid, form H 2 gas; stable in w eak base

N aB H 3C N : stable at pH 5-6

hygroscopic, dried self, suggest: buy sm all am ount each tim e

(G rignard reagent)

H 2O

M g / Et O JO C , 1969, 34, 3923.

H

B r

N a / N H 3; Li / N H 3; N a / EtO H Zn; Fe; Sn; M g

(3). m etal reduction

(2). hydride reduction

(1). free radical reduction

JA C S, 1972, 94, 8905.n -B u 3SnH H

B r

N aB H 4 / InC l 3 / C H 3C N

radical reagent

n -B u 3SnH / A lB N

JAC S, 2002, 124, 906.

i iii N aB H 3C N

i LiA lH 4

i ii ii N aB H 4

ii TH L, 1969, 3095.

JO C , 1976, 41, 3064.

iv LiB H Et 3 (super hydride)