_Student_METODICHKA1(Full).pdf

7/22/2019 _Student_METODICHKA1(Full).pdf

1/29

. ..

. ..

.. , ..

1

, ,

2005


2/29

2

547.917, 547.918

24.239

M31

: ..., . .. (. .. )

.., ..

. 1. , ,

., . .. , 2005

-. ..

.

. 235/2005.

, ,

.

, .

,

. ,

550800

070100

. . . , 2005


3/29

3

4

1. 4

2. 10

3.

14

3.1. 14

3.2. 14

3.2.1. 15

3.2.2. -

16

3.2.3. N- 17

3.3. 19

3.3.1.

19

3.3.2. 21

3.3.3. 22

3.4. 23

3.5.

25

28


4/29

4

,

. .

(), ,

.

,

. ,

,

, .

1.

() (),

.

- , .

. , , ,

. , ,

, , , ..

, .

,

, .

,

, .

nH2nOn (1).


5/29

5

, .

,

, ; (2),

2--2--4---5--.

HCOH

HCOH

HCOH

HCOH

CH2OH

OH

HCNH2

HCOH

HCOCH3

C

CH2OH

OH

OHH3C

1 2

19 , ,

. .

, , ,

,

.

, , n ,

2n

,, (1) 16 , -.

,

, . .

(

D- ,

)

, , -

,

,

,

. ,

, ,

, .

H

H

C

HOH2C

CHO

HOCH2

CHO

OH

OH


6/29

6

,

.

, , . ,

.

(3, 4),

.

OH

CHO

H

CH2OH

H

CHO

HO

CH2OH

3 4

3D-, 4

L- . ,

, ,

D,

L-.

D- L-

, .

, D-,

,

D-.

O

CH2OH

HO

H OH

H

CH2OH

OHH

O

CH2OH

H

HO H

OH

CH2OH

OHH

D-

D-

OH

CHO

H

H

H OH

CH2OH

OH

OH

CHO

H

CH2OH

H

CHO

HO

H

H OH

CH2OH

OH

OH

CHO

H

HO

H OH

CH2OH

H

OH

CHO

H

H

H OH

OH

CH2OH

OHH

OH

CHO

H

HO

H OH

H

CH2OH

OHH

H

CHO

HO

HO

H OH

H

CH2OH

OHH

OH

CHO

H

HO

HO H

H

CH2OH

OHH

D-

D-

D-

D-

D-D-

D- D-


7/29

7

, ,

,

,

.

, . , ,

,

,

.

, .

, .

(

), , ,

.

.

5a

5b

O5

4

3 2

1O

4

3 2

1

HO

O

OH

OH

OH

5

4

3 2

1

OHH

HO

H OH

CH2

H

OHH

5

4

3

2

1

O

(5)

(5b), , , 5b , (5)

, .

,

(-5).

, ,

(6b6c).

6b 2 , ,


8/29

8

-5, 2-5.

66d,

,

.

O

OH

OH

OHHOCH2OH

1

23

4

5

6b 6d6c

OH

CHO

H

HO

HO H

H

CH2OH

OHH

D-, 6a

OHH

HO

HO H

C

H

HHO

CH2OH

H5

4

3

2

1

OHH

HO

HO H

CH

H

HHO

O

HOH2C

1

2

3

4

5

O

.1.

,

:

1. , , -5

-4 , ,

L-, ,

D-.

2. 2- -5 -4 , ,

D-, , L-.

(-1)

,

, .

,

-1 , - -. D-

, - . L-

. -

,

D- L- ,

- . ,

, ., -4.


9/29

9

OH

OH

OHOH

-

-

O

OH

OH

OHHOCH2OH

OH

C

H

HOHO H

H

CH2OH

OHH

OH

D-

O

OHOH

OH

HOCH2OH

D-

D-

OHH

HO

HO H

C

H

HHO

CH2OH

H

O

OHH

HO

HO H

C

H

OHH

CH2OH

H

O

,

,

,.

, ,

, , .

O

OH

OH

CH2OH

HO

HO

O

OH

OH

CH2OH

HO

HO

O

OH

OH

CH2OH

HO

HO

O

OH

OH

CH2OH

HO

HO

-D--D- -D- -D-

. 2.

,

, , .

, ,

. , .

,

.

. , D-

, .

, . , -D-,

D-.


10/29

10

OH

CHO

H

HO

H OH

H

CH2OHOHH

OHH

HO

H OH

H

CH2OH

OHH

HO OH

HO

O

OH

OH

OH

CH2OH

HO

O

OH

OH

OHCH2OH

O

OH

OH

OH

HO

OHCH2

O

OH

OH

HO

HOCH2

OH

-

60.2%

-0.21%

-39.4%

-0.20%

D-,

0.0024%

0.0077%

.3.D-

2.

-

. ,

,

.

, . -

,

. ,

, ,

, .

. -


11/29

11

, ,

.

O54

32

1

O

5

4 3 2

1

O

5

4 3

2

1

O

54

3

2

1O5

4

3

2

1

O5

4

3 2

1

O

5

4

3

2 1

O

5

4

3

2

1

4C1

1C45,2B

3,0B

4,1B

B4,1

B5,2

B3,0

. 4.: , -

,

(, 1,5B), , (4

1). , (14

41)

:

1.

.

,

-1 14

41.

O

a

a

a

a

e

ee

e

eO

eee

e

ea

a

a

a

a

2. , , .

2 ,

,

.

3. ,

, ,

-2 -4 -1 -3 .4. -2 ,

-1 , -1 -2,


12/29

12

, ,

(2-).

75% - (25%

-).

ae e

eaOH

HOHO

O

OHOH

ae e

e eOHHO

HOO

OHOH

H

OHOOH

HC3

-D- -D-

5. -1

,

-1 ( ).

, ,

.

Br Cl OCOR OCH3 SR OH NH2.

X

O

a

X

Oe

,

, .

-, - -

41 (D). D

1

4 , .


13/29

13

a

e

e

ee

HOHO

HOO

OH

OH

a

a

ee

eHO

HOO

OH

OH

OH

ae

ee

HOHO

O

OH

OH

OH

a

e

e

e

e

a

OH

OHO OH

OH

OH

e

e

e eHOOHHO

HOO

OH

e

a

e

ee

a

OH

OHO OH

OHOH

ae

eeHO

OHHO

O

OHOH

e

a

e

e

e eOHHO

HOO

OHOH

HO

O

OH

OH

OH

CH2OH

-D-

HO

O

OH

OH

OHCH2OH

-D-

HO

OOH

OHCH

2OH

OH

-D-

HO

OOH

OH

CH2OH

OH

-D-

-D-

O

OH

OH

OHCH2OH

OH

-D-

O

OH

OH

OH

CH2OHOH

-D-

O

OH

CH2OH

OH

OH

OH-D-

OOH

CH2OH

OH

OH

OH

,

,

.

(

envelope ), ( twist ).

,

.

.

,

-2 -3, ;

.

O1

2

34

O 1

2

3

4

2E

3T2


14/29

14

3..

3.1. .

.

,

, (

, , ),

,

.

, ,

. ,

: ,

.

.

, .

(Ac),

(Bz), (Bn) (All),

,

. ,

N-, N- (Pht) N- (Z)

NH2-.

3.2. .

(Ac) (Bz)

.

.

, O- S-,

.


15/29

15

.

. ,

, ;

.

. -

-

,

.

. , (NaOMe MeOH) .

.

3.2.1. .

.

.

6-

,

.

(, 1--1H-)

(1).

1

HOHO

O

OH

OMe

OH 1. Bu2SnO

2. BzCl

HO

BzO

O

OH

OMe

OH

HO

BzO

O

OBz

OMe

OH

(53%) (21%)-D-


16/29

16

( 2). -D- (7), ,

6-- (Tr) (8) 6---

(TBDMS) (10) , -6

3-- (9) 2---D-(11) .

2

HOOH

HOHO O

OH HO

OH

HOHO

O

OTr

HOOH

OHO

O

OH

O

HOOH

HOHO

O

OTBDMS

OOH

HOHO

O

OH

O

1. CH3CH2CH2COOH,

Chromobacterium viscosum2. H+/H2O

1. CH3CH2CH2COOH,

Candida cylindracea2. Bu4NF

TrCl

TBDMS-Cl

7

8 9

1011

3.2.2. -

.

,

.

-

, .

. (- ),

. ,

( 3).

.


17/29

17

3

BzOOMe

BzO

O

OHBzO

HOOMe

HO

O

OHOH

BzOOMe

BzO

O

OBzO CH2Cl

O

1. ClCH2COBr, -50oC,

2. BzCl H2NC(S)NH2

,

,

.

(3()22-),

,

, ,

. -

, -2

, -2

,

. ,

-2 2-()(CAMB)

2-(2-) (CAEB) .

. CAEB,

, , , .

3.2.3. N-.

N-

. , 2--2-

-

(4).4

N

O

O

ROHN

O

O

ROHN

O

O

XRO

X -

,

,

( 5).


18/29

18

, , ,

().

5

H2NSEtRO

ROO

OR

OOSEtRO

RO

O

OR

N

2--2-

,

:

1. (TCP)

;

2. (Dts) ;

3. 2,2,2-(Troc) (

);

4. ,

.

,

, -D-(6).

-

(Tf)

, -2 .

6

HO

OH

AcOAcO

OAcO TfO

OH

AcOAcO

OAcO

OH

AcOAcO

OAcO

N3

NaN3Tf2O, Py

OH

AcOAcO

OAcO

H2N

H2/Pd

. ,

H2S .

, N-.


19/29

19

3.3. .

()

, .

,

. ,

( Bn ) / .

,

.

,

-3 ,

-4 , (

1 4-),

OH-.

3.3.1. .

, ( ) (

) , ,

. -

. ,

2,6---,

TfOH.

( 7).

,

4,6-O-- (12) 6--

4-O-

. , LiAlH4 AlCl3 4,6--

(12) 4-O- (13). 4-O-

, 3-

.


20/29

20

7

HO

R2OR3O

O

OH

OR1

R2OR3O

O

OR1

O

O

Ph

HO

R2OR3O

O

OBn

OR1BnO

R2OR3O

O

OH

OR1

PhCH(OMe)2, H+

12

13 14

LiAlH4, AlCl3 NaCNBH3, HCl

4,6-O- (12) NaCNBH3

HCl 6-O- (14).

6-O-

N- , , .

-TfOH.

6--

4,6-- ,

.

Pd-.

( ,

, ).

, -(PMB),

,

2,3--5,6--1,4-(DDQ)

. , PMB-,

, ( -

-),

DDQ, . PMB

,

, , -.


21/29

21

-

.

(Tr)

. -

( ) 6--

(8),

5-O-.

8

HO

HOHO

O

OH

OHAcO

AcOAcO

O

OTr

OAcAcO

AcOAcO

O

OH

OAc

1. TrCl, Py2. Ac2O H

+

,

,

,

2,4,6---.

, ,

, , HBr ,

.

3.3.2. .

, ,

(NaH). ,

, ,

Pd(0)-

(9).

9

Pd(PPh3)4

HOHO

O

O

O

SiO Si

OR1O

O

O

O

O

O

O

O

O

SiO Si

OR1O

O

O

O

O

SiO Si

OR1

O Cl

O

,

. ,

,


22/29

22

( 10).

- ,

.

, ,

Pd-, Rh- Ir-.10

RO ROH

tBuOK H+

RO

. ,

, ,

HgO/HgCl2.

3.3.3. .

,

,

-(TBDMS),--(TBDPS)

1,1,3,3--1,3- (TIPS) .

,

. , TBDMS- TBDPS-

, TBDMS-

TBDPS. ,

.

TBDMS- TBDPS-

(11).

11

HOOMeHO

O

OHOH

BzO

OMeBzO

O

OTBDPSBzO

BzO

OMeBzO

O

OHBzO

BzCl

Bu4NF

HO

OMeHO

O

HO OTBDPS

TBDPS-Cl,

.


23/29

23

, , HCl MeOH

MeOH.

1,1,3,3--1,3- (TIPS)

, -. 3,5--TIPS-

4,6--TIPS- ( 12),

.

4,6-O-TIPS , ,

3,6-O-TIPS-

. TIPS-

HF.

12

HO

HO

O

OH

OBn

HO

HOHO

O

O

OBn

O

SiO Si

BzOBzO

O

O

OBn

O

SiO Si

BzO

BzO

O

OH

OBn

O

Si

OSi

F

BzOBzO

O

OH

OBn

HO

BzCl

HF, Py

TIPS-Cl

Bu4NF

3.4. .

-

.

.

:

1. -,

2. -,

3. , ,

( ). ,

, , .


24/29

24

( )

1,3-

, 4,6--

. 1,3-

, ,, -.

, -D- (15) 4,6-O---D-

(16)

3,4-O---D- (17)

-(13).

13

1516 17

6

7

18

19

HOHO

OOH

OMe

OH

HOHO

O

OMe

OOPh

HOHO

O

OH

HO

OH

OO

O

OH

O

O

O

OH

OH

CH2OHOH

OH

O

O

O

CH2OHO

O

HOHO

O

OH

HO

OH

O

O

O

O

O

OHO

OH

OH

OH

HO

OHCH2

CH3COCH3, H2SO4

Me2C(OMe)2, H+

PhCHO, ZnCl2

CH3COCH3, H2SO4

HO

OOH

OMe

O

O

,

, ,

. D- (6), - ,

(18), D- (7),

-,

(13). , D-(7)

1,2;5,6---

-D-(19).

-

.

(,

)

. ,


25/29

25

,

.

3.5.

,

. ,

,

( 14).

. ,

2,3,4,6-----D- (21) 2,3,4,6----D- (22)

HCl.

14

7 20

21 22

BnOOMe

BnOBnO

O

OBn

BnOBnOBnO

O

OBn

OH

OHOMe

HOHO

O

OH

OHOHHO

HOO

OH

HCl

MeOH, H+ BnBr

( 1,6-

)

(15).

4C1 1C4,

(, D-) , .

15

NaOH

AcOAcO

O

OAcOR

OAc

1. RCl2. Ac2O, H

+

a

HOHO

O

OH

OPh

OH

e OHO

OH

O

OH

(Ac, Bz), ,

.

(16), .


26/29

26

, (Bn) (All),

.

Pd-,

.

.

- (TBDMS),

,

(

).

2- ,

(16).

16

HOHO

O

OH

O

OH

HOHO

O

OH

OHAcO

AcO

O

O

O

O

AcOAcO

O

OAc

OH

Ph

HO

HO

O

O

O

O

HOHO

O

OH

OTBDMS

Ph

BnOBnO

O

O

O

O

TBDMSOBnO

O

OBn

OBn

Ph

BnOBnO

O

O

O

O

HOBnO

O

OBn

OBn

Ph

1. PhCH(OMe)2, H+

2. Ac2O

3. (NH4)2CO3

1. TBDMS-Cl, Im2. NaOMe, MeOH

BnBr, NaH

Bu4NF


27/29

1.

-

AcCH3

O

Ac2O/AcONa,AcCl/

N2H4*H2ON2H4/AcOH

Bz

O

/MeONa/MeOH,

NH3/MeOH,Et3N/MeOH

ClAcClCH2

O

,-

2-(2--)

()

CAEB ClCH2

O

O(CH2)2

O

-

.

2,2,2--

-TCE

Cl3CCH2O

O

-

-

AllocO

O

-Pd(0)-

LevCH3 O

OO

N2H4*H2O

Bn CH2

/NaH NaOH, KOH, Ag2O

H2, Pd/CNa/NH3, O3, RuO4

-- PMB CH2CH3O --DDQ,

, TfOH

- Tr (Trt) Ph3C--/

NaHH

+ H2, Pd/C

All / NaHt-BuOK +,

Pd(0)

--

TBDMS Si

-/

Bu4NF, HCl/MeOH,BF3/MeOH

--

TBDPS Si

Ph

Ph

-/ //

1,1,3,3---1,3-

TIPS

SiO

Si

iPr

iPr iPriPr

1,1,3,3---1,3-

//

- Me2C

/ H2SO4,-/

TsOHH

+

CH

/ TsOH

H+-

,LiAlH4 6-OH-NaBH3CN 4-OH-


28/29

28

1. , . .. .., 2, .: , 1976.

2. . , , .: , 1975.3. .. ,.. , .. ,.. , .. , .. ,

, .: , 1967.4. .. , .., .. , , .: , 1978.

5. Carbohydrate chemistry, Ed. by G.-J. Boons, Blackie Academic & Professional, 1998.6. Carbohydrates. Structures, synthesis and dynamics, Ed. by. P. Finch, Kluwer

Academic Publishers, 1999.


29/29

1

, ,

-..

_________ 6084/16. .

. . . 1. 100 .

______

03507 (. 003792) 221

. ...

-.119571 , . 86.

_Student_METODICHKA1(Full).pdf

Documents

Transcript of _Student_METODICHKA1(Full).pdf