Toward the development of a general chiral auxiliary. Enantioselective alkylation and a new catalytic asymmetric addition of silyloxyfurans: application to a total synthesis of (-)-rasfonin

Robert K Boeckman Jr; Joseph E Pero; Debra J Boehmler

doi:10.1021/ja063532+

Toward the development of a general chiral auxiliary. Enantioselective alkylation and a new catalytic asymmetric addition of silyloxyfurans: application to a total synthesis of (-)-rasfonin

J Am Chem Soc. 2006 Aug 30;128(34):11032-3. doi: 10.1021/ja063532+.

Authors

Robert K Boeckman Jr¹, Joseph E Pero, Debra J Boehmler

Affiliation

¹ Department of Chemistry, University of Rochester, P.O. Box 270216, Hutchison Hall, Rochester, New York 14627-0216, USA. rkb@rkbmac.chem.rochester.edu

PMID: 16925414
DOI: 10.1021/ja063532+

Abstract

An enantioselective total synthesis of the apoptosis-inducing natural product, (-)-rasfonin, is described. Camphor lactam-mediated asymmetric alkylation reactions enabled the installation of three stereogenic centers with >95:5 diastereoselectivity. A modified Corey-Peterson olefination was employed in the construction of the (E,E)-diene system. A highly diastereoselective, asymmetric vinylogous Mukaiyama aldol addition was conducted using a chiral cationic oxazaborolidine catalyst. The pyranone core of the natural product was prepared via a DBU-promoted rearrangement of a furanol to its corresponding pyranol with concomitant [1,4]-silyl transfer.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

Alkylation
Catalysis
Fatty Acids, Unsaturated / chemical synthesis*
Fatty Acids, Unsaturated / chemistry
Furans / chemistry*
Pyrones / chemical synthesis*
Pyrones / chemistry
Stereoisomerism

Substances

Fatty Acids, Unsaturated
Furans
Pyrones
rasfonin