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Synthesis 2010(18): 3126-3130  
DOI: 10.1055/s-0030-1257859
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Total Synthesis of Two Isoflavone Bis-C-glycosides: Genistein and Orobol 6,8-Di-C-β-d-glucopyranosides

Shingo Sato*, Hidetoshi Ishikawa
Graduate School of Science and Engineering, Yamagata University, 3-4-16 Jonan, Yonezawa-shi, Yamagata 992-8510, Japan
Fax: +81(238)263120; e-Mail: shingo-s@yz.yamagata-u.ac.jp;
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Publication History

Received 14 April 2010
Publication Date:
16 July 2010 (online)

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Abstract

This paper describes the first successful synthesis of two isoflavone bis-C-glycosides, genistein and orobol 6,8-di-C-β-d-glucopyranosides from phloroacetophenone bis-C-glycoside in total yields of 27 and 19%, respectively, using a four-step reaction: direct C-glycosylation of phloroacetophenone with unprotected d-glucose; chalcone synthesis by aldol condensation; acetal synthesis by oxidative rearrangement using DIB and p-TsOH; and formation of the isoflavone ring using HCl, without protection of the glucose moiety.

Key words

bis-C-glycoside - isoflavone - DIB - p-toluenesulfonic acid - oxidative rearrangement

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13

These compounds were inseparable without AcOH in the solvent system owing to their instability.