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Synthetic Communications: AnInternational Journal for RapidCommunication of SyntheticOrganic ChemistryPublication details, including instructions for authors andsubscription information:http://www.tandfonline.com/loi/lsyc20

Unsaturated Sugars : AnAlternative Route to 3, 5, 6-Trideoxy-1, 2-O-Isopropylidene-α-D-Glycero-Hex-3, 5-DienofuranoseS. Achab a & B. C. Das aa Institut de Chimie des Substances Naturelles, C.N.R.S. ,91190, Gif-sur-Yvette, FrancePublished online: 06 Dec 2006.

To cite this article: S. Achab & B. C. Das (1982) Unsaturated Sugars : An Alternative Routeto 3, 5, 6-Trideoxy-1, 2-O-Isopropylidene-α-D-Glycero-Hex-3, 5-Dienofuranose, SyntheticCommunications: An International Journal for Rapid Communication of Synthetic OrganicChemistry, 12:12, 931-938, DOI: 10.1080/00397918208061929

To link to this article: http://dx.doi.org/10.1080/00397918208061929

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SYNTHETIC COMMUNICATIONS, 12(13) , 931-938 (1982)

U N S A T U R A T E D SUGARS : A N A L T E R N A T I V E R O U T E T O

3,5,6-TRIDEOXY-l, 2-2-ISOPROPYLIDENE-a-D-GLYCERO-

HEX-3,5-DIENOFURANOSE

S . A c h a b a n d B . C . Das

I n s t i t u t d e C h i m i e d e s S u b s t a n c e s N a t u r e l l e s , C . N . R . S . ,

9 1 1 9 0 G i f - s u r - Y v e t t e , F r a n c e .

U n s a t u r a t e d s u g a r s a r e among t h e m o s t i m p o r t a n t

a n d u s e f u l c o m p o u n d s i n c a r b o h y d r a t e c h e m i s t r y . T h e y

a s s u m e k e y r o l e s i n t h e s y n t h e s i s o f m o d i f i e d s u g a r s

a n d c o m p l e x n a t u r a l p r o d u c t s . T h e t i t l e compound 2, a n

u n s a t u r a t e d s u g a r c o n t a i n i n g a c o n j u g a t e d d i e n e s y s t e m ,

h a s b e e n r e p o r t e d ' r e c e n t l y a n d i t s p o t e n t i a l s y n t h e t i c

v a l u e f o r D i e l s - A l d e r r e a c t i o n g i v i n g a c c e s s t o f u n c -

t i o n a l i z e d a n n u l a t e d f u r a n o s e s h a s b e e n p o i n t e d o u t . L

F o r a d i f f e r e n t s y n t h e t i c p u r p o s e w e p r e p a r e d t h i s com-

pound by a n a l t e r n a t i v e r o u t e a l b e i t f r o m t h e same

s t a r t i n g m a t e r i a l u s e d b y t h e p r e v i o u s a u t h o r s . Our

s y n t h e t i c s e q u e n c e is o u t l i n e d i n t h e f o l l o w i n g s c h e m e .

931

Copyright 0 1982 by Marcel tkkker. Inc.

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932 A C W AND DAS

i, P h 3 P , E t 0 CN-NCO E t ,Phf f ; i f , 3 - M e t h y l - 2 - s e l e n o x o - 2 2 b e n z o t h i a z o l e, C F3C02H, C H 2 C 1 ; iii, (CF S O ) 0, P y r i d i n e ; 3 2 2

i v , D B U , E t 2 0 .

C o m m e r c i a l l y a v a i l a b l e 1,2-2-isopropylidene-a-D-

g l u c o f u r a n o s e (I-), w h i c h c a n a l s o b e r e a d i l y o b t a i n e d

by s e l e c t i v e h y d r o l y s i s o f 1 , 2 , 5 , h - d i - 2 - i s o p r o p y l i d e n e -

a - D - g l u c o f u r a n o s e , w a s d i r e c t l y c o n v e r t e d t o 5 , 6 - a n h y d r o -

1,2-~-isopropylidene-~-D-glucofuranose (2) i n 8 5 % i s o l a -

t e d y i e l d . The o n e - s t e p t r a n s f o r m a t i o n o f 1 t o 2 w a s

a c h i e v e d by t h e u s e o f t h e triphenylphosphine-diethyl

a z o d i c a r b o x y l a t e s y s t e m r e c e n t l y f o r t h e

s y n t h e s i s o f e p o x i d e s f r o m v i c i n a l d i o l s . T h i s c o n s t i t u t -

e s t h e s i m p l e s t r o u t e t o t h e e p o x i d e 2 . D e o x y g e n a t i o n o f

t h e 5 , 6 - o x $ r a n e r i n g o f 1. a c c o r d i n g t o a known p r o c e d u r e

w h i c h m a k e s u s e of 3-methyl22-selenoxo-benzothiazole a n d

t r i f l u o r o a c e t i c a c i d i n d i c h l o r o m e t h a n e s o l u t i o n l e d t o

5

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UNSATURATED SUGARS 933

t h e o l e f i n 3. T r i f l u o r o m e t h y l s u l f o n a t i o n o f 3 w i t h

t r i f l i c a n h y d r i d e i n d i c h l o r o m e t h a n e s o l u t i o n a t -1O'C

i n t h e p r e s e n c e o f p y r i d i n e g a v e t h e t r i f l a t e k i n 9 6 %

y i e l d a f t e r c o n v e n t i o n a l i s o l a t i o n . E x p o s u r e o f t h e

t r i f l a t e e s t e r t o D B U i n d r y e t h e r s o l u t i o n a t room

t e m p e r a t u r e l e d t o e l i m i n a t i o n o f t r i f l i c a c i d a f f o r d -

i n g 3 , 5 , 6 - t r i d eo x y- 1 , 2 -0- i s o p r o p y l i d e n e-a - D - g l y c e r o - h e x - 3 , 5 - d i e n o f u r a n o s e ( 5 ) i n q u a n t i t a t i v e y i e l d .

T h e e l e c t r o n i m p a c t mass s p e c t r u m o f 2 showed a n

i n t e r e s t i n g f r a g m e n t a t i o n . T h u s , b e s i d e s t h e m o l e c u l a r

i o n ( m / z 1 6 8 ) a n d t h e M-CH3(m/z 1 5 3 ) p e a k s , t h e m a s s

s p e c t r u m showed a n i n t e n s e f r a g m e n t i o n p e a k (m/z 1 3 9 )

d u e t o l o s s o f C H O ( h i g h r e s o l u t i o n ) f r o m t h e m o l e c u l a r

i o n . T h i s u n u s u a l f r a g m e n t a t i o n may b e e x p l a i n e d b y

t h e f o l l o w i n g m e c h a n i s m i n v o l v i n g a r e a r r a n g e m e n t ( s e e 6)

o f t h e f u r a n o s e a n d t h e

5 -

i s o p r o p y l i d e n e r i n g s y s t e m s .

CHO

6 m/z 1 3 9 -

A l s o , t h e p r e v i o u s l y r e p o r t e d ' 'H N M R a n a l y s i s o f

- 5 w a s i n c o m p l e t e . T h e c o m p l e t e a n a l y s i s o f t h e 4 0 0 MHz

'H NMR s p e c t r u m b a s e d o n s p i n d e c o u p l i n g e x p e r i m e n t s i s

g i v e n i n t h e e x p e r i m e n t a l s e c t i o n .

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9 34 ACHAB AND DAS

T h e p r e v i o u s s y n t h e s i s ' o f 2 r e q u i r e d t h e c l e a v a g e

o f t h e C ( 5 ) - C ( 6 ) bond f o l l o w e d by a W i t t i g o l e f i n a t i o n

w h e r e a s a l l t h e o r i g i n a l c a r b o n s o f g l u c o s e a r e r e t a i n -

ed i n t h e f o u r - s t e p p r o c e d u r e p r e s e n t e d h e r e .

EXPERIMENTAL

A l l m . p . s were d e t e r m i n e d o n a K o f l e r h o t - s t a g e

a p p a r a t u s . 'H NMR s p e c t r a o f d e u t e r i o c h l o r o f o r m s o l u t i -

o n s w i t h M e S i a s i n t e r n a l s t a n d a r d ( 6 = 0 ppm) were

t a k e n o n a V a r i a n T-60 a n d o n a B r u k e r WH400 s p e c t r o -

m e t e r . T h e e l e c t r o n i m p a c t m a s s s p e c t r a (EIMS) were r u n

o n a n AEI-KRATOS MS50 s p e c t r o m e t e r a n d a m o d i f i e d A E I MS9

i n s t r u m e n t w a s u s e d f o r r e c o r d i n g c h e m i c a l i o n i s a t i o n

m a s s s p e c t r a (CIMS) f o r w h i c h i s o b u t a n e w a s employed

a s t h e r e a c t a n t g a s . O p t i c a l r o t a t i o n s w e r e d e t e r m i n e d

o n a J o u a n a n d R o u s s e l Q u i c k p o l a r i m e t e r . T h i n l a y e r

c h r o m a t o g r a p h y (t.1 .c .) w a s d o n e o n s h e e t s p r e c o a t e d

w i t h s i l i c a g e l 60 (HF 2 5 4 , Merck) t o a t h i c k n e s s o f

0 . 2 5 m m . F o r c o l u m n c h r o m a t o g r a p h y , M e r c k s i l i c a g e l 60

(0.063-0.20 mm 70-230 mesh ASTM) w a s u s e d .

4

T r i p h e n y l p h o s p h i n e ( 6 5 5 mg; 2 .49 mmol) was a d d e d t o

a s t i r r i n g s u s p e n s i o n o f 1,2-g-isopropylidene-a-D-gluco-

f u r a n o s e ( 5 0 0 mg; 2.27 mmol) i n d r y b e n z e n e (25 m l ) i n

t h e p r e s e n c e o f 3A m o l e c u l a r s e i v e s u n d e r a n i t r o g e n

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UNSATURATED SUGARS 935

a t m o s p h e r e a n d t h e m i x t u r e w a s s t a r t e d t o r e f l u x . A f t e r

d r o p w i s e a d d i t i o n o f d i e t h y l a z o d i c a r b o x y l a t e ( 4 3 5 mg;

2 . 4 9 mmol) i n a s o l u t i o n o f d r y b e n z e n e (1 m l ) t h e r e a c -

t i o n m i x t u r e w a s r e f l u x e d f o r 2 . 5 h . T h e s o l u t i o n w a s

c o o l e d t o room t e m p e r a t u r e a n d t h e n l e f t o v e r n i g h t a t

5 O C . T h e p r e c i p i t a t e w a s f i l t e r e d o f f a n d t h e f i l t r a t e

e v a p o r a t e d t o d r y n e s s . T h e r e s i d u e w a s c h r o m a t o g r a p h e d

o n s i l i c a g e l . E l u t i o n w i t h h e x a n e l e t h y l a c e t a t e ( 3 / 2 )

a f f o r d e d 2 ; y i e l d : 3 9 0 mg ( 8 5 % ) ; R f ( 3 : 2 h e x a n e : e t h y l

a c e t a t e ) : 0 .25 ; [ a JD : - 2 5 " 5 1 , c h l o r o f o r m ) ; l i t .

&]io : - 2 6 . 5 " ( 5 4 , H 2 0 ) ; m.p

2 5 6

1 3 3 " ; lit! m . p . 1 3 3 . 5 " .

EIMS : m/z 1 8 7 (M+'-CH3), 1 6 9 ( 1 8 7 - H20), 1 5 9 (M+ ' -C2H30) .

CIMS : m/z 2 0 3 ( M H + ) .

'H N M R ( 6 0 MHz) : 6 = 6 (6, 1 H ; H - 1 ; J = 4 H z ) ; 4 . 5 (d, 1 H ; 1 , 2

H-2; J = 4 H z ) ; 4 . 2 7 ( g , 1 H ; OH) ; 4 . 0 7 (IU, 2H; H - 3

a n d H - 4 ) ; 3 . 4 (m, 1 H ; H-5 ) ; 2 . 9 (t, 2H; H - 6 ) ; 1 . 4 7 a n d

1.31 ppm ( 2 2 , 3 H e a c h ; 2 C H 3 ) .

2 9 1

5,6-D i d eo xy- 1 , 2 - 0 - is0 p r o p y l i d e n e - a - D - x y l o - hex- --------- -- ---- ----- --------- ------------- 5- eno f u r a n o s e (A) -_--_--------

3-Methyl-2-selenoxobenzothiazole ( 1 . 2 4 g ; 5 . 4 4 mmol)

a n d t r i f l u o r o a c e t i c a c i d ( 6 2 0 mg; 5 . 4 4 mmol) were

a d d e d t o a c o o l e d (OOC) a n d s t i r r e d s o l u t i o n o f 2 (1 g ;

4 . 9 5 mmol) i n d i c h l o r o m e t h a n e ( 5 0 m l ) . A f t e r 5 h a t

room t e m p e r a t u r e t h e r e a c t i o n m i x t u r e w a s n e u t r a l i z e d

w i t h s o d i u m b i c a r b o n a t e , f i l t e r e d a n d t h e f i l t r a t e

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936 A C W AND DAS

e v a p o r a t e d t o d r y n e s s . T h e r e s i d u e w a s c h r o m a t o g r a p h e d

o n a c o l u m n o f s i l i c a g e l . E l u t i o n w i t h h e x a n e l e t h y l

a c e t a t e ( 3 1 2 ) g a v e t h e o l e f i n 3 ; y i e l d 7 0 0 mg ( 7 6 X ) ;

Rf ( 3 : 2 h e x a n e l e t h y l a c e t a t e ) : 0 . 3 5 ; a n a n a l y t i c a l

s a m p l e was c r y s t a l l i z e d f r o m EtOAc; m.p. 6 8 ' ; l i t . 5

m.p. 7 0 " ; E 3 i 5 : - 6 0 " (2 1 , c h l o r o f o r m ) ,

'gH14O4 C a l c . C 5 8 . 0 5 H 7 . 5 8 0 3 4 . 3 7

Found 5 8 . 2 2 7 . 5 0 3 4 . 6 0

EIMS : m/z 1 7 1 (M+'-CH3); C I M S : m/z 1 8 7 (MH+).

= 4 H z ) ; 1 3 2

'H N M R ( 6 0 MHz)

5 . 7 6 - 5 . 2 6 (my 3H; o l e f i n i c p r o t o n s ) ; 4 . 7 5 (g, 1 H ; H - 4 ) ;

: 6 = 5 . 9 5 ( c l , 1 H ; H - 1 ; J

4 . 6 0 (A, 1 H ; H-2; J = 4 H z ) ; 4 . 1 0 (A, 1 H ; H-3; 2 3 1

J = 2 . 5 H z ) ; 2 . 0 (2 , 1 H ; O H ) ; 1 . 5 8 a n d 1 . 3 8 ( 2 2 , 3H

e a c h ; 2 CH3).

3Y2

A s o l u t i o n o f 2 ( 2 8 0 mg; 1 . 5 mmol) i n d r y d i c h l o -

r o m e t h a n e ( 1 5 m l ) was c o o l e d t o - 1 O O C u n d e r a n i t r o -

g e n a t m o s p h e r e w i t h s t i r r i n g . To t h i s s o l u t i o n p y r i d i -

n e ( 4 8 0 1.11; 6 mmol) w a s a d d e d f o l l o w e d b y a d r o p w i s e

a d d i t i o n o f t r i f l i c a n h y d r i d e ( 3 0 0 u l ; 1.8 mmol) .

A f t e r l h a t - l O ° C t h e r e a c t i o n m i x t u r e w a s t a k e n w i t h

d i c h l o r o m e t h a n e ( 1 0 m l ) a n d w a s h e d s u c c e s s i v e l y w i t h

i c e - c o o l e d a q u e o u s s o l u t i o n s o f s a t u r a t e d s o d i u m

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h y d r o g e n c a r b o n a t e , 0 .5N H C 1 a n d b r i n e . T h e o r g a n i c

p h a s e w a s d r i e d o v e r s o d i u m s u l f a t e a n d w a s t h e n e v a -

p o r a t e d t o d r y n e s s . T h e r e s i d u e w a s t a k e n w i t h h e x a n e

( 2 x 1 5 m l ) , f i l t e r e d a n d e v a p o r a t e d to d r y n e s s t o g i v e

t h e t r i f l a t e 5 a s a n o i l ; y i e l d

h e x a n e l e t h y l a c e t a t e ) : 0 . 5 5 . An a n a l y t i c a l s a m p l e w a s

c r y s t a l l i z e d f r o m p e n t a n e ; m.p. 4 4 " ; [a]

: 420mg ( 9 6 % ) ; R f ( 4 : 1

2 5

D - : - 2 8 ' ( ~ 1,

CHC13).

C10H13F306S C a l c . C 3 7 . 7 3 H 4 . 1 2 S 1 0 . 0 7

F o u n d 3 7 . 9 9 4 . 1 1 1 0 . 2 2

E T M S : m / z 3 0 3 (M+'-CH3); CIMS : m / z 3 1 9 (MH').

= 4 H z ) ; 'HNMR ( 4 0 0 M H Z )

5 . 8 0 ( m , 1 H ; H-5;

5.53 ( 5 , 1H; H-6 ' ; ' 6 ' , 5

1 9 2 : 6 = 6 ( 4 , 1 H ; H - 1 ; J

= 1 1 H z ; J g S 4 = 5 H z ) ; 5 9 6

= 18Hz, J

= 1 8 B ~ ) ; 5 . 4 3 ($, 1H; H-6;

' 5 , 6 '

= 2 . 5 H z ) ; 4 . 7 8 394

J 6 , 5 = 1 1 H z ) ; 5.08 (is 1 H ; H-3; J

= 2 . 5 H z ) ; 4 . 7 3 (is 1 H ; H - 2 ; 4 9 3

( b r o a d i, 1 H ; H-4; J

J = 4 H z ) ; 1 . 5 1 a n d 1 . 3 3 ( 2 2 , 3H e a c h ; 2 CH3). 2 , 1

1 , 8 - D i a z a b i c y c l o ~ ~ . 4 . ? ? u n d e c - 7 - e n e ( 3 0 0 ~ 1 ;

1 . 9 8 mmol) was a d d e d d r o p w i s e t o a s t i r r e d s o l u t i o n

o f ( 4 2 0 mg; 1 . 3 2 mmol) i n d r y e t h e r ( 1 5 m l ) u n d e r a

n i t r o g e n a t m o s p h e r e . A f t e r b e i n g l e f t o v e r n i g h t a t

room t e m p e r a t u r e , t h e r e a c t i o n m i x t u r e w a s t a k e n w i t h

e t h e r (10 n i l ) a n d w a s h e d f i r s t w i t h i c e - c o l d wa te r

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938 ACHAB AND DAS

a n d t h e n w i t h c o o l e d 0.1N H C 1 f o l l o w e d b y b r i n e . T h e

o r g a n i c l a y e r w a s d r i e d o v e r s o d i u m s u l f a t e a n d e v a p o -

r a t e d t o d r y n e s s t o a f f o r d 1. a s a s y r u p ; y i e l d : 1 0 0 % ;

R ( 4 : l h e x a n e l e t h y l a c e t a t e ) : 0 . 6 3 ; [ a ] i 5 - 1 7 7 " ( f 3 . 4 ,

c h l o r o f o r m ) ; l i t . [a$' - 1 4 9 . l o ( c _ 1 . 0 6 , c h l o r o f o r m ) .

EIMS : m/z 1 6 8 ( M + . ) , 153(M+'-CH3), 139(M+ ' - CHO).

'H N M R ( 4 0 0 MHz)

J 5 , 6 '

f 1

= 11Hz; 596

: 6 = 6 . 1 8 ( d d Y 1 H ; H-5; J - - = 5 H z ) ; 5 .70 ( a _ , = l 8 H z ) ; 6 . 0 9 ( d , 1 H ; H - 1 ; J

1 , 2 = 1 1 H z ) ; - 6 9 5

1 H ; H-6 ' ; J 6 , , 5 = 1 8 H z ) ; 5 . 3 2 ( d , 1 H ; H-6, J

5.30(*, 1 H ; H-2; J = 2 . 5 H z ) ; 5 . 1 5 ( a _ , 2Y3

= 5Hz; J 2 , 1

1 H ; H-3; J = 2 . 5 H z ) ; 1 . 4 5 a n d 1 . 4 3 ( 2 5, 3H e a c h ;

2 CH3).

3 9 2

A C K N O W L E D G E M E N T : We a r e g r a t e f u l t o M r . J . - P . C o s s o n

f o r v a l u a b l e t ec hn i c a i a s s i s t a n c e.

REFERENCES

1. K . M . S u n a n d B . F r a s e r - R e i d , S y n t h e s i s , 2 8 , ( 1 9 8 2 ) .

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