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Synlett 2010(15): 2247-2250  
DOI: 10.1055/s-0030-1258024
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

N-2-Glycosyl Thiosemicarbazides from N-3-Glycosyl Oxadiazolinethiones Obtained from 2-S-Glycosyl Oxadiazolines via Mild Thermal S→N Migration of the Glycosyl Moiety

El Sayed H. El Ashry*a,b, El Sayed H. El Tamanyc, Mohamed R. E. Alyd, Ahmed T. A. Boraeia
a HEJ Research Institute for Chemistry, International Center for Chemical and Biological Sciences, Karachi University, Karachi, Pakistan
Fax: +20(03)4271360; e-Mail: eelashry60@hotmail.com;
b Chemistry Department, Faculty of science, Alexandria University, Alexandria, Egypt
c Chemistry Department, Faculty of Science, Suez Canal University, Ismailia, Egypt
d Chemistry Department, Faculty of Science, Taif University, Saudi Arabia
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Publication History

Received 1 June 2010
Publication Date:
09 August 2010 (online)

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Abstract

A new class of N-2-glycosyl thiosemicarbazides has been synthesized from N-3-glycosyl oxadiazoline-thiones. Glycosylation of 5-(1H-indol-2-yl)-1,3,4-oxadiazolin-2(3H)-thione with acetylated α-glycosyl halides by grinding in the presence of basic alumina gave the S-glycosyl oxadiazoles while in the presence of Hg(II) chloride N-3 glycosyl analogues were obtained. In the presence of Et3N or K2CO3, mixtures of S- and N-glycosylated isomers were obtained as products. The S→N glycosyl migration under catalyst-free mild thermal conditions was described, and a new class of N-2-glycosyl thiosemicarbazides was synthesized from N-3-glycosyl oxadiazolinethiones by ring cleavage of the oxadiazolole ring by treatment with ammonia in methanol.

Key words

indolyloxadiazolines - S-glycosides - N-glycosides - glycosylation - thiosemicarbazides - thermal rearrangement

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Experimental Procedure
The S-glycoside 5 (0.5 mmol) was fused under atmospheric conditions, and the thermal conversion was monitored by TLC. After completion of the reaction (5-10 min), the fused mass was crystallized from EtOH to afford the corresponding N-glycosides 8. A mixture of 8 (5.0 mmol) in MeOH (10 mL) and NH3 solution (32%, 5 mL) was stirred at 0 ˚C for 1 h, then allowed to reach ambient temperature. After 6 h, the solvent was evaporated in vacuo, and the residue was purified by column chromatography (EtOAc-MeOH-CHCl3 = 4:3:3) to give 11; mp 212-214 ˚C.