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Synthesis 2002(14): 2105-2109
DOI: 10.1055/s-2002-34380
PAPER
© Georg Thieme Verlag Stuttgart · New York

The Carbohydrate-Sesquiterpene Interface. A Zirconocene-Mediated Synthesis­ of (+)-Epiafricanol from d-Glucose

Leo A. Paquette*, Ruslan M. Arbit, Jacques-Alexis Funel, Sergei Bolshakov
Evans Chemical Laboratories, The Ohio State University, Columbus, Ohio 43210, USA
Fax: +1(614)2921685; e-Mail: paquette.1@osu.edu;
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Publication History

Received 7 June 2002
Publication Date:
26 September 2002 (online)

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Abstract

A total synthesis of (+)-epiafricanol (6) has been readily achieved from d-glucose. The tricyclic alcohol target was arrived at by first forming methyl 6-O-benzyl-2-deoxy-2-C-methyl-α-d-altropyranoside (12) and converting this intermediate into methyl 2-C-methyl-2,3,4-trideoxy-α-d-threo-hexopyranoside (14). There followed a series of steps resulting in extension of the side chain to give the isopropenyl pyranoside 9. This advanced intermediate was subjected to zirconocene-promoted ring contraction, which gave rise to 8 and set the stage for conversion to 7. This tertiary carbinol was transformed into 6 by sequential ring-closing metathesis and stereodirected Simmons-Smith cyclopropanation.

Key words

zirconocene - metathesis - ring contraction - glucose - sesquiterpene

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The authors thank John Hofferberth for these calculations.