Carbohydrufe Research, 43 (1975) 19.5499 0 Elsevier Scientific Publishing Company, Amsterdam - Printed in Selgiurn

Note

Synthesis AFANASSI

of uracil

nucleosides

of D-xyluronic

acid derivatives*

AKHREM,VICXOR A. TIMOSHCHLJK,AND IGOR A. MIKHAILOPULO

A.

Institute of Bioorganic Chemistry, ByeIorussian S.S.R. Academy of Sciences, Min.& (U.S.S.R.) (Received June lSth, 1974; accepted for publication in revised form, February 12tI-1, 1975)

The isolation of nucleoside antibiotics’ containing aminodeoxy and unsaturated derivatives of uranic acids has stimulated interest in this class of compound_ The

nucleoside fragments of these antibiotics, as well as of various analogues, have been synthesised, and many of these products display significant physiological activity2. We now report on the synthesis of I-(methyl 2-O-acetyl-3-U-toluene-p-sulphonyl-/?-D-xylofuranosyluronate)uracil (4). Selective, acid hydrolysis of 1,2:5,6-di-0-isopropylidene-3-O-toluene-p-sulphonyl-a-D-glucofuranose ’ followed by oxidation of the resulting 1,2-O-isopropylidene-3-O-toluene-p-sulphonyl-~-D-glucofuranose successively with potassium periodate and permanganate yielded 1,2-O-isopropylidene-3-O-toluene-psulphonyla-D-xylofuranuronic acid (1). Aqueous acetic acid was used as solvent for the second oxidation step in order to prevent elimination of the tosyl group4, and the use of sulphurous acid5 for dissolution of manganese peroxide simplified the isolation and markedly improved the yield of 1.Treatment of 1 with ethereal diazomethane gave the ester 2. The n.m.r. data (Table I) of 2 are characteristic of the structure (cJ ref. 6). Compound 2 was unexpectedly resistant to acetolysis; an acetic acid-acetic anhydride-sulphuric acid mixture containing 20% of sulphuric acid was necessary to effect the conversion of 2 into syrupy methyl 1,2-di-U-acetyl-3-O-toluene-psulphonyl-D-xylofuranuronate (3), which was shown by n.m.r. spectroscopy to be a 0

IF

NH

I

R%‘=

o

O--:Mq lR=

H

2R=

Me

*Modified and T. E.

M-c@*o

“‘-i)--

q.

OAt 3

M’“*c+$)-q_c’

OAC 4

OAC 5

Nucleosides:Part II. Part I: A. A. Akhrem, N. I. Garbuz, G. V. Zaitseva, I .A. Mikhailopulo, Prokofyev, TetraJzedron,in press.

SPECTRAL

DATAa

H-l

4.90ut

606ut

5.14ud

6.20ud

7 (CD&)

8 (CDC13)

4.70ud

5.26uq

6.44d

5.09d

5.4Oq

5.82d

5.89d

H-5

U?UCil

7.24d

8.04d

H-6

AcO MePh

2.16s AcO 3.90s COOMe

186s 2,38s

9.64s ’ NH

2.16s AcO 250s MePh 3.92s COOMe

250s . MePh 3.46s COOMe

Ofhers

5.5

3.5 2.5

65

4.4

3.2

Synthesis of uracil nucleosides of D-xyluronic acid derivatives.

Carbohydrufe Research, 43 (1975) 19.5499 0 Elsevier Scientific Publishing Company, Amsterdam - Printed in Selgiurn Note Synthesis AFANASSI of uraci...
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