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Synthesis 2005(18): 3167-3178  
DOI: 10.1055/s-2005-918428
FEATUREARTICLE
© Georg Thieme Verlag Stuttgart · New York

A Divergent Synthesis of Triyne Natural Products and Glycosylated Analogues Using a Carbenoid Rearrangement

Thanh Luu, Wei Shi, Todd L. Lowary*, Rik R. Tykwinski*
Department of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2, Canada
Fax: +1(780)4928231 ; e-Mail: rik.tykwinski@ualberta.ca; e-Mail: tlowary@ualberta.ca;
Further Information

Publication History

Received 23 July 2005
Publication Date:
25 October 2005 (online)

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Abstract

Using a carbenoid rearrangement to introduce the conjugated acetylenic framework, a series of triynols has been synthesized in five steps from 1,4-butynediol. Several of the triyne alcohols are known natural products and others are glycosylated analogues. This route avoids the use of terminal diynes as precursors, which can be unstable and/or difficult to prepare. It is therefore procedurally attractive in comparison to more traditional routes such as the Cadiot-Chodkiewicz and Sonogashira coupling reactions.

Key words

polyacetylenes - polyynes - carbohydrates - Fritsch-Buttenberg-Wiechell reaction - carbenoids - natural products

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1

The term polyyne is meant to denote compounds with a structural sequence of two or more consecutive (conjugated) acetylene units. The term polyacetylene has been often used in this context as well, but this term can be ambiguous due to its more common use in reference to polymerized acetylene.

10

For a review of recent polyyne syntheses, see: Shi Shun, A. L. K.; Tykwinski, R. R. Angew. Chem. Int. Ed., in press.