Stereoselective Formation of a Functionalized Dipeptide Isostere by Zinc Carbenoid-mediated Chain Extension

Abstract

The application of a zinc carbenoid-mediated chain-extension reaction to a functionalized peptide isostere is reported. The cleavage site of human CVM protease was utilized as a target for testing the synthetic methodology. The utility of this chain-extension reaction is demonstrated in the preparation of an amino acid-derived α-unsubstituted γ-keto ester, which is incorporated into a framework that mimics a tetrapeptide. The identification of a suitable protecting group strategy facilitated the application of a tandem reaction for the incorporation of an α-side chain, and the use of an oxazolidinone auxiliary provided excellent diastereocontrol in a tandem chain-extension−aldol reaction. Stereoselectivity of the tandem chain-extension−aldol reaction was determined through application of a CAN-mediated oxidative cleavage reaction.

Department

Chemistry

Publication Date

1-16-2009

Journal Title

Journal of Organic Chemistry

Publisher

American Chemical Society

Digital Object Identifier (DOI)

10.1021/jo801993k

Document Type

Article

Rights

Copyright © 2009, American Chemical Society

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