A new route to 6-deoxy-6-halo sugars

TetrahedronLetters No.29,pp. 2517-2518,1970. PerWon

ALxlom6m M.L.

Shulman,

Press.

Printed in Crest bitah

6-Dmx-6-EAmsm3bRs VJIT.

Yoldikovand

Institmtofor Chalatry

LYa.

Khorlla

ofl!TaturalEh3&ot6,

USSR Aoadoq of Soionoem,Homoou,USSR (Receivedin UK 6 May 1970; acceptedfor publication21 ISsy1970)

Dirootreplaoement of a bpNlgrorrp,by athea exoeptingatananomerio

logmated mgara of interast

a halogenatorinwgardorlv-

oentreis oonvenlentaethodofprogariag

aa reaotive intomediate

ha-

and a8 potantialmta-

bolio inhlbitoro. Howwer relatiro1JI~feu reagentmare availablefor thi8 p Wehavefeund, thatthePlnnarrmaotlon (3) provideaa new mute genated mugarm. lar

ease

in

subatit\ienta

mm s#

roaotion(4) had beenahown

to

halo-

to prooeedwithpartioa-

oaso of iddate hydrohalidee oontainingeleotronlooeptirrg

the

in

the

idno

aydhad8

inaanoelnthe

acid reeidue. The reaotloa ha# been u8d si. oertaln a1~1halideaviaunatablo

wht5,6)s aoetimidate ROE+ cc1

F

for

triohloro-

..

+mia1-

{cc13c(mml)oR~ a

U~iagpartlal~prataot~baxaswdth

__,

mal + cc13cmE2

free~bpdEog1

alooholoorponentofthoruotion wehave obtainad

,gpaspu

theoorru~~

q-64~~10 sugarsingoodyi.lQ. 9%0 gemmlprooedumls

as tilloua.Th~proteotederr~andCCl~

ohloroformaolutioni8saturatedrith~dro~halido

in

at-15°.Afterhcqing

the sealedreaotionmirture at room tempera*rofor 1045 hour0 (EBr) or for

@Cl) and rmoving the volatileooqmunda and CC13COBE2the pro&et

2 -6

ie

lrrolated by ohroma&rapby. Inthie uayweha~e ~tihoaiwdmetbyl

2,3,4-trl4-aoet+6-ohloro-6-

-4'~- oc-IhgluoopJzFam~do (I)(7) in s&JOB yield6,mop* 97=98O, [+y +l~“(oO.l,

+

ohlorofolli),met&yl2,5,4-tzLO-ao~l-6-bromo-6-daoxy-or-D25i7

2518

-gluoonymzloride .(a 0.1,

(II)(') 3.n

ehlorofoa),

me-1

77-7s",

(III)(*)in 77% sold, a+

-aid. fors)and

[e]$O

+ 53' (0 0.1, ohlom-

b~l2caoukd&-3,edi~o~l~~~,~d~~u-~u(IV) in 75% yield,mr& 134435'.

o~mido

: C&9.79

roforr). Caloulatad for Cl+2@W7

+ IW

*F [I

I H,5.28 ; Bq17.44.

m

I:x = Cl

(0 0.2, ohloM:

IE

EX=mr ,

Bsrs

drastio

oonditiona

are rocpirod

[email protected]

1.

for

aubstitntlon

of a seoon~

in the progreeeof lnvrntigation.

J.&O. Baznett, Advan.CarbohM. Chem.,@, 183 (1967).

2. 8. Ikaesaianand I.B. Flesaas, J. OCR. Chom.,a 3. A. Pbmer,

DioImi&&hor

und ihzv

I

, 2163 (1969).

r

Derivate, Berlin,1892; R. Roger and

D.6. Beilsom, Chem,ROVE.,a, 186 (l%l). 4. 8.Y. IUlvaln and B.S. 'pate, J. Am. Chem.Boo.,a, 2233 (1951). Llohtenthaler,Chem.Ber., p3, 1555 (1958). 5. P. Cramer,K. Pauelsikand JF.W. 6. Y.L. Shulmam,Q.4. Sbrekhgomr and B.A. Uftakhova,

231. Ox%?.Khlm-, 3,

874 (1967). 7.

B. Eelferioh,W. Klein and W. S&or,

8. F. Vale&in, Coll.Cwoh. Chem.Co-.,

w.,

a, 79 (1926).

p, 354 (1934).