A Synthesis of Jaspamide Based on 1,2-Metallate Rearrangements of α-Heteroalkenylmetal Derivatives

Philip Ashworth; Brian Broadbelt; Pawel Jankowski; Philip Kocienski; Austen Pimm; Richard Bell

doi:10.1055/s-1995-3870

Synthesis 1995; 1995(2): 199-206
DOI: 10.1055/s-1995-3870

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A Synthesis of Jaspamide Based on 1,2-Metallate Rearrangements of α-Heteroalkenylmetal Derivatives

Philip Ashworth, Brian Broadbelt, Pawel Jankowski, Philip Kocienski^* , Austen Pimm, Richard Bell

^*Department of Chemistry, The University, Southampton, SO17 1BJ, UK

Abstract

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Jaspamide (Jasplakinolide), a marine cyclodepsipeptide, was synthesised from tripeptide fragment 4 and (2S,4E,6R,8S)-8-benzoyloxy-2,4,6-trimethylnon-4-enoic acid (3). The tripeptide fragment was prepared from β-tyrosine derivative 6, Boc-2-bromoabrine (8), and alanine. β-Tyrosine derivative 6 was prepared by asymmetric conjugate amination of methyl p-hydroxycinnamate. Bromabrine derivative 8 was prepared from tryptophan. Key steps in the synthesis of the polyketide fragment 3 include 1,2-metallate rearrangement of a metallated dihydropyran and a metallated enol carbamate derivative.

cyclodepsipeptide - Jaspamide - antifungal - 1,2-metallate rearrangement - higher order cuprate - enol carbamate

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