Synthesis of 5-O-β-D-galactofuranosyl-D-galactofuranose

Curboh\drate Cl Elwvwr

Sc~enrdic

Rzsmrch.

SYNTHESIS

OF

59 (1977) 51-86

Publ~,h~ng

Cornpan)

Amsterdam

- Prlnrrtd

In Belgium

5-O-/I-D-GALACTOFURANOSYL-D-G,\L4CTOFl_IRANOSE

IBSTRACT

Conversion amlno)benzylldene] select~le

ring

openIns

INTRODLIC

The title dl>sccharlde

I-I-D-palactol’urano\e

type-jprcltic

RWbLrS

HO-3.

and

I-~/&D-

from 4 b\ reaction

orthoacerarc)

D-gaiactofuranoid

by the lsolailon

f4lo~\ed

\rlth

hv remwal

unlr> In ollgosaccharldes

has

of 5-0-/?-D-glucop>rano~yl-D-galactofursno~e’ from

of Pnrumococcus

a \ynthejls

33B and

partial

acid

hvdrol\

of the latter dl\xcharlde

A%D DISCCISSIOX

benz\l

ment of D-galactoss

s/~-D-~alactofuranosldc diethi

and chlorld$ cr!,stalllne

The ‘H-n

m r spectrum

proton3

at

Hz,

rS -1

H-IS)

bcnz>l

and

a doublet

quantlficatlon

(Jl

Z 3-4

3 4 Hz)

Hz,

cnnralned

H-l I).

wa’~ rentatllely

assigned

hy the pro\lmlrv

slpnsls

as ob>erved

to H-l

for

mlkture.

syrup,‘.

(I?“h)

>lnglet

(J,

Z

6-amInohex>

A small doublet

of the x-pyranosldc. for the hcnzyl

of rcsonJnczs

I

from

ior dnomerIc

up of an overlspplnp

for at lesbt 90” r) ol’rhe

and accountlrg

itas hampered

made

of mcrcurlc

are frequently

has been Isolated4

wlpho\lde-cIO

form\,

In the presence

by thl< method

G-D-_ralactofurano,lde

9 for rhr furdnobe

D-galnctofurano4e5. dt 0 4 73 (J,,?

obtaIned

of I In meth)I

In 61”~ \ wld b\ trr’dt-

l I) \t_n prepared

L\.1111ken?\ I alcohol

I dlthoacrtal

Furanwde,

although

-0

I ?-(methyl

of (I --) 5kllnhed

substance

report

Syrup! o\lde

and

?.3-dl-O-xrtyl-6-O-henzok

was bynthejtjed

5-0-P-D-galactofuranos!,i-D-pal~crofur~no~c~

Iye n(w

5.6-O-[r-(illmethyl-

HO-Z

TION

been demonstrated thr

the

oi

groups

The occurrence and

Into

by xer>latlon

. sake benzyl

of the xctsl

(4)

3.4 6-trl-0-acet)

followed

derlvatl\c.

~alactofurano~ldc of prolccrinp

r~-D-gaiaclofuranosldr

oT hen31

but

II~

methylene

proup the procedure

of Hanesslan

excess of N.lV-dlmeth)lbenzamlde

Follo~\~og

dlmethbl

(t I c ) of two dlaStereonlerIc ap-o-galactofuranosidc

forms

of benzyl

(2) in \irtunlly

and klorallo@u”. acetal

1 I~JS treated

In chloroform

to

gl\e

:!

kilrh an mlkture

5.6-O-ir-(d~methylam~no)bcnz)‘l~dcoc]-

quanrltati\c

bleld

Rescrlon

of 2 \rlth

acetic

82

I!’

, F)‘= + .,

4

G

J. VISER,

J F G

\‘I_.EGEWH4RT

c-c.

h,G3= 8:

AC,R2=

R’ =

3

dnhydrlde

In p]rldlne

R

=

Ai

rhe 2 3-dwcelak

aHorded

3 which

~111 aqueous

ben7yi 2 3-di-O-~cet~l-6-O-benzoyl-~~~-D-_palactofur~nos~de

of 63”,1 ~a> obrarnsd lsolared of the

for Ihe sequence Compound

groups

wa\

m r. spsc~rum

Condrnsallon t\lth

(5)

.ICtfI~t2)-

dcacvla[lon

of

of

the

Irnpurlrae~

ga\c (6)

that

\tere

In the

of 7 aas

cantnlnlps resdllv

revealed

chromatography. I.?-(methli

of

which

Alrhougll

,lfter

not and

coiumn

m r

wlrh

5-O-/.?-D-galacto-

one

spot

which

conromlnsnts

(‘H-n

ortho-

bromide.

benzgl 6 @ale

The

rcsldues

bv Ion-eNchange

mercuric

dcbenzyl.Uion

(7)

galacrop~rano~c schle\ed

from

~solarcd

ylcld

\\ere

slructure

presence

.I ml\ture ad>

S-O-ll-o-~al~ctofursno~yl-o-=onlactofurnno~~ dlbacchsrldes

by column

3.S.6-trl-O-acetvi-r-D-Ealactofurnnoje

product.

ncer~c sad.

An o\crall

losses due to the lah111tj

In considerable purltied

~~rh the aaged

-I in nlrromethanr

I‘uranosyl-D-gdlactofuranoslde contained

4 was

consistent

(4)

I -+ 2 -, 3 -, 4 IS hen Ihe Intermcdlates

to purlfq 12 and 3 rcsultcd

Attempt3 5.h-accta~

its ‘H-n

cation

H

P7=R’=H

D,ra.-laS

3t2

HEESN’IJK,

R. VAN

in I I c.

pave \\cre

specrroscopv)

IL

mainI} reducing Pu~rfi-

chromatographya

I

h

c

I J

The stop>,

presence

alrhough

of the (I -+5)-l~nbagc

assignment

the basis of 3 X0-hlHz

in 7 H;~S confirmed

of the furanold

spectrum

anomcnc

protons

by ‘H-n MS

onlv

m r. spectroposslblc

on

DISACCHARIDE

physical

The o-palactttol

constants

18). obtatned

those reported Reductton

of

llnhage

In

7 wth

sodtum

rctentton

5-O-l)-D-galactoluranosyl-

of 7 corresponded

ttmes of trtmethylstlylated

(co-chromatography)

horodeutertde

and acetylatton

closely

followed

gale

The

I c -m s and proved

bq g ‘i-l-n

zlycostdtc

m r

and

opttcal

syn-

by

methvlatton”

and

I.~dt-O-acetvl-~.3.~.6-tetra-O-

the

rotation

to

(see E\pertmental)

snd 5-0-acetyl-I.7.3.~.6-penta-~-methyl-D-~a~actitol-/-~~

ldrnrlfied 7

Intersugar

reductton

The

and Spencer’

rrductton.

methyl-o-galactttol’(9) were

borohydrtde

8 tn g I c !iere tdentrcal

to hydrolysts

kshlch

of 7 and those of crystalhne

upon

by Gortn

thettc and authenttc then”

53

SYNTHESIS

presence

data

of

(IO),

CI I’urnno>)I

(1 -5)-

for 7 and 8 e4nbltshed

the

Itnha,ge to be /I

CHOOhqe

CH,OAc

I

HCOMe

117 HOAc

. 101 -

s205

MeOCH

In1

MeOCH ^__

‘1,_--+---MeOcH

--7T

,E’_ \

I hCOAi

Cenwal

-

5-O-P-o-Galactofuranosl-D-_enlactltol

Py rtdtne (I Ittre) was purtlicd

Jnd hept over molecular Soluttons

\iere

at ambient

‘H-Nmr.

spectra

HX-360

SIZW

(360 hlHz)

(DSS)

methylsted

their

datn

recorded

on

a Jeol W-AN’

accelerattng

boltage

dertIaIt~es’ wth SE-30

-

tn the

3 hi’.

Itteraturc3

me-h)

tontztng

at

detector

and glass columns

on Chromosorb Rctcntton

W-AW

times

hlass

wth

(10

pol~rtmcter Brukr

2.2-dtmethyl-2for the prepara(75 eV)

of

of

300 of

SE-30

( Ts) are

gilen

on

250

trtmethl

a Pye !04 tnstrumrnt (SO-100

of ltcrc

tzmpernrure

G I c.

’

ltere

and

lstl! I

equtpped

( I 60 m y -I mm) pached wth DMCS

ml)

e;lrlwr’

spectra

, Ion-source

300 /IA]

P A J

for the tnferpretatton

[column

15s

current

Dtrecttons and

Ii)

combtnatton

(8&100

I-II

(90 hlHz) or sodtum

btandard hr\ttols

Dr

rotatton>

model

tctr;lmethylstlane

as the tnternal

gt\en

DhlCS

of 30 mllmtn

,a-u

aad

ais descrthed

Spec~tic

E41-390

[‘arun

wth

purified

a Perhtn-Elmer

\\lth

JGC-IOO;JhlS-07

or 3Ob of OV-I7

\ias

per-O-acetylated

are

from chlorosulphcntc

x I-l mmH_r

’ of sugars \%a3 cart-red out at 227

finme-tontsatton

flow-rate

irtth

recorded

tton of parttally

Chromosorb

40 (b‘tth)

spectrometers.

stlapentane-5sulphonate g I c -m s

at

temperature

were

was a ptft from

by dt\ttllatton Nttromcthane

S4

concentrated

dctermtned

r r( ,

,a,,

10

9

Gortn

123

3

890

of

mesh) and ‘1 nttrogcn

rcldtt\c

to that

of

hle,St-

sucrose. T I c. was performed FR-1500)

All reactions

on stltca gel (Schlstcher

were monitored

SC Schull

TLC

by t 1 c . and mobtltttes

Ready

Plastx

are expressed

as

FOI!

R,.

whore

S

detected

u v

denotes

a reference

by charrln_g wth

light

(25-l nm)

Kx~elgcl

Column

3301oc)

ho.

compound

sulphurlc

3 startIn:

Benzyl

with

(25 I),

materral

derlkatlvcs

chromatography

me>h)

chloroform-methanol

or

acid

\\ere

was performed

The

on

~IIIC~

benrrne-propan-3-ol-~~~ter

4,

spots gel

(30

were

under

also detected

(hlercb

13 I).

B.

C. chloroform-methanol (lo0 I), D. actz~c acld-eihyl F, ethyl acetate-acetic acid-water

acetate-butan-I-ol-\rat~r (6 3 S I), E, water. (9 2 2). and C. propsn-?-al-ethyl acetate-water

(5 5 7)

D-yaiacro:ttrattosrd~

(1) - The crhdr svrup~ product4 ~35 purl&d bt column chromatography (solvent -i I The firbt fraction \\;lb concentrated se\ersl times I‘rom Its sihanollc solur~on to rcmoie wldual solvent -1and yielded I aj a 3~rup (K!"o). Btn-_ll

[xJD

-23

(L

I.

mcchanol)

g I c of the hlc,S~ ‘H-l\:

dsta

m T

The material

dcrlvatl\c

(methyl

gabs one spot III t I c (solkent>

pans one peal\

sulphotldwl,)

with

;i shoulder

L) 7 Z-7 S (m,

5 H.

aromatIc

(m.O9H..I, z -0 and 3-4 Hz. H-IS and H-lx of ruranosldcs). H-I ~(1) of pyrano,ldc]. and ? 3-l S (other proton,) [Found C. 57 70. H, 6 67

chloroiorq

(20 ml)

components diluted $olutlon

dried (Na,SO,).

filtered.

(3 5 ml

migrating

nbdrogen

rehldue

tempsrarurs

elutlon.

J,,

(I Iltrc)

on

and

solicnts

7 3-8

HO-5.

C. 62 8s.

H, 5 72:;)

and

t Ic

mlpratlng

WI> cooled.

the orpnnlc

and

laber \\a>

to _ IO ml a! 30 (bath)

\ilth

chlorororm

three

To tht

(SO ml. 0 ) extracted

for 2 h and

then

and pyrldlne

times

In acetic xld-iiatsr

poured

vU;?se\tracted (4) and four

dls appeared and bznzql-CH?)

Into

upon

aquzoub

The

residual

minor

product

Ph),

m r

sbrup consisted han.lng R,

chromatopraphb

011 (3 75 g. 8 Id mmol. dsta

(chloroform-J)

2 0 (5. 6 H.

2 4~0).

deuterium-ewhange).

(Found

C. 63 il

sodium

(3 A 200 mi)

components

by column

‘H-N 5 H.

8’L

chloroform

3s a colourle~~

(L 4. chloroform) 7 3 (m,

The

!ilth

4 U;~S purified

B) and obtslnsd

therefrom

with

\!;is rsmoisd

( I9 I. 40 ml). and the so1ut1on

Jnd concentrated

2 (2 m. 5 H. OBz).

5 S Hz,

solution

and

Jnd concentrated.

component

C -

(m. 3 H. sugar ring protons talc

diluted

(Nua,SO,)

-36

I6 h.

closeI!,

of I

sddcd follo~~ed bv acetic t I c (solvent B) re\ealed the I’ormatlsn of equal ;imounts and (3. R 2 2 5) In approximately

0 YO Compound

1). [xlD

I)

21 h

The ml \:urc

B) of ;1 maJw

L) 7 1-7 6 and I H.

;Ind concentrated

Atkr

of t\io

The

(SO ml).

of toluene

dljsol\sd

was dried

>ol\rnt

based

~a>

b> e\aporntlon

carbonnrs

I 33. 086.

(gradlent

(d,

freeze-dried

temperature

amounts

w--\\8ter

ml1 dried ;It 0 (Na,SO,L

(Ml

dnd the citrsct c .

Aiier

solution

7 g) \{a~ Immsdwelu

I 79.

4.73 [d, ,I,,-, 3.4 Hz. (for

(Xl ml) was Immedlatelv

pyridlnc

components

The

\\;1> hept at room

69’;

2”).

37 mmol)

nt room

the formation

equal

(SO ml) and

closely

the

1 and

of

-I 9

H. 6 71”b]

in th< darh

chloroform

the ab>ence of3 tcc-~~dtct

AIrred

the cbbcnce

(conraInIng

.lnh\drldc

(t I

C. 57 77,

at Ii’, 4 In clppro\lmdtslj

\\lth

-sp;lratcd.

from

\\a>

B) revealed

(solLent

(3’.

talc

slope

protons),

Btittz I I .?,3-A-O-u( r~ I /-t5-04wtt~o I f-D-y(ifuc-folttrunojt(~=, (4) - A ml lture I I 8 mmol). A IV-dimethylbcnz~mlde Ulmethyl acetalh (5 ,a. 25 h mmol).

(3 2 g

t\!o

CIIHIYOCl

A and G). cind

on rhe negatl\e

H. 5 96

and

3 23

3 S-j

CzJH2_OJ

Y

86

\\‘. A.

showed

the

presence

of

R. \AN

HEESWlJh,

galactosc

and

‘O of S-d, was in accordance

analysis’

Ii

G

galactltol

J. VISSER,

F. G.

VLIEGENTI-LART

Aldltol

I I ratio

IIY a

wth the awgned

J

acetate

structure

4ChNO\\LEDG&lENTS

We hlr

C

Lhnnk

Versluls

recording

hlr

G

(Laboratory

360-MHz

Netherlands

Foundat,on

Netherland>

Orpanlsatlen

View publication stats

Geralg

for

01 Analytical

the mash spectra. and hlr

the YO- and

REFERENCES

J

‘H-n

m r

A

ChemMry,

V E George

spectra

for Chcmlcsl

conducting

This

Research

for th2 Advancement

the

methnnolysls

State and Dr

Unl\erslty, L. Dorland

lnbestlgatron (S 0 N ) \\Ith of Pure

euperlments. Utrecht)

was supported financtal

Research

for

for recording by the

ald from the

(Z W 0 )