22

.
.
.

 . .
, . , .
. - -
.
: ,
, .
.
;
. .
.
, .
.

H3 N

H3N

COO

COO
H
CH2
CH3

H
CH3

H3N

CH3

COO

COO

COO

H3N
H

H
CH3

H3N

H3C

CH3

OOC

H2N

CH2
CH3

COO
H3N

H
CH2

COO

COO
H3N

H3N

H
CH2

CH2

HN
OH


COO

COO
H3N

H
CH2OH

H3N
H

COO
H3N

OH

CH2

CH3

SH

COO

COO

H3N

H3N

CH2
CH2
S
CH3

COO
H3N

CH2
H2N

CH2
CH2

O
H2 N

COO

COO
H3N

H3N

CH2

CH2

COOH

CH2
COOH

H 3N

H2N

CH2

CH2

CH2

CH2

CH2

CH2

CH2

NH

NH2

COO

COO

COO

H2N

H3N

H
CH2
NH
N

NH2


- -c

HCl

NaCN/NH4Cl
H2N

O
R1
O

R2 NaCN
H2O

R1

R2

HO

CN

O
R2

OH
NH2

(NH4)2CO3

R1
-

R1

OH H

H2N

CN

R2

HN

COOH

R1

R2

H2N

CN
CO2

O
NH
O

R1

R2

HN

CN

COOH

H
N
Ph
H

Ph
O
H
O
NaCN/NaHSO3
NC

Ph
H

HO
O

76 %

SMe
SMe
O
NaCN/NH4CO3
MeS

O Ba(OH)2

HN
NH
O

H2N

83%
O
OH


O Et
O

O Et
O

HNO2

Et

O Et

Et

H2/Pd

N
OH

O
O

Ac2O

O
Et

NHAc
O

O Et

O
O

O Et

Br

Et

NHAc

Et

O
O

O Et
O

O
O

55 %

Br

O
NHAc

AcHN

O Et
Et

NHAc

NHAc

NHAc
HO

Et
O
O

OH

O Et

O Et
O
Et

KOH

HN
O

N2H4

HO

R
HO

O
HNO2
O

O
R

OH

KOH O

NH2

N3

NH
R

NH2

HO
O

HO
O

O Et

O Et
RI/EtONa O

NHNH2
N2H4

NC

NC

O
NC
HNO2

Et
O

OH KOH

N3

O
NH

NH2

R
NC

O
EtOH

R
NC

O
OH

O Et
O

NaN3

Cl

Br2, PCl3

OH

NH3, EtOH

NH2

O Et
O

H2/Pd

O Et
O
H2N

N3
O

28%

LDA
O

NH2OMe

NH2
O
OH
55%

NH2

O
OH
O

OH

NH4Br
NaBH3CN

O
49 %

NH2

NNHPh
OH
O

OH
O

H2/Pd

OH
O
87 %

Ph
O

H2N

Et

Ph
NH

Ph

N
Ph

Et

O
PhCH2Br
NaOH
Bu4NCl
Ph

Ph
Ph
O

H2N
O

Et

N
Ph

Et


O
O

Br

N
C

NC

NaH

O
Et

NaH
N

NC

Et

Et

O
O

Et

O
NC

Et


O
O Et
O

O N

O N

O Et
Ph
OH

O N

O Et
Ph
H2/Ni O

O N
O

O
H2/Pd

BnBr
EtONa
O

Ac2O

O Et
Ph

H2N

O Et
Ph

O
H2N

H2/Pd

O Et
Ph
OH

O
H2N

O Et
Ph


0.2 mol%
[ClRh(C8H14)2]2

H2, EtOH, C6H6

1 bar, 20 C
HO2C

NHCOMe

HO2C

NHCOMe
72 % e.e. (R)

CH2PPh2

O
CH2PPh2
BF4

Ph
Me
Me

PPh2

MeO

Rh

P
Ph2

S,S-CHIRAPHOS
89 % e.e. (R)

P
Rh
P

Ph
MeO
R,R-DIPAMP

 - -
OH

Ph

NH2

OH

NH2OH
Ph

NH4OAc

O
OH

30-40 %
OH
O
O

Et2NH

Et

TMSO

OH

Et

99 %

O
NK

Cl

CN

H2SO4

O
NHBoc BuLi
CO2

H2N

CN

OH
47-62 %

OH
NHBoc
55 %

(Boc)2O
OH

NH2

NaOH

Et

Cl
O

O
OH

Et3N

Et

NHBoc

NHBoc

CH2N2
O
O
BocHN

OH

N2

Ag
H2O

NHBoc

MeS

+
H2N
CO2H

H2N

CO2H

MeS

N
H

H
N
O

H2N
O

1
R

N
H

H
N
O

N
H

CO2H

H 2O
H H

H
H3N

C N

R O

H
2

COO

COO + H3N

H3N
R

COO
R

X
Glu

Cys Gly

Glu

Cys Gly
Glu-Cys
Cys-Gly

NH2

H
N

HOOC
O

O
N
H
SH

Glu-Cys-Gly

OH
O

O
COO

OH
+
OH
O

H3N

HO
+

HO

H
CO2 + R
O

O
N

O
O

 .
( )
N

S
O
+

Ph
HN

NH-
H2N

OH

S O
NH-
HN

Ph

Ph
H+
Ph
N

S
O

PhHN

HN
Ph

O PhHN
H+
Ph

S
N

OH
NH-
Ph

R
NO2

H2N
H

O2N

HOOC
NH

NH

NO2

R
O2N

1--2,4-

2,4-

COOH
O

O
O

CH3

NH O

H2N

HO

CH3

Dansyl chloride
SO2Cl

CH3
N
CH3

N N

Dabsyl chloride

SO2Cl

O
H2N

O
OH

MeOH

H2N

SOCl2

O
DCC

O
H2N

OH

Boc2O

BocHN

OH

HN
O

BocHN
S

 ()
O
H2 N

O
OH

MeOH
SOCl2

H2N

O
O

Ac2O

AcNH

N2H4
O

O
O
AcNH

R
N
H

AcNH
CO2Me

N3

HNO2

AcNH

N
H

NH2

(%)


96.0 %

99.8 %

11

66

98

21

44

96

31

29

94

51

13

90

100

1.7

82

. (B. Merrifield 1921-)

1984

O-

N
H

O
O
O

O
R1
NH2

N
H

O
O

R
N
H

OH
O

TFA

+ H2N

R1
N
H

O
R

NH

HF

N
H

R1

Cl

R
N
H

O
O

- (. , . 1951.)

. (L. Pauling 1901-1994)

1954

- ()
( )

- ( )