Synthesis and determination of the absolute configuration of (-)-(5R,6Z)-dendrolasin-5-acetate from the nudibranch Hypselodoris jacksoni

I Wayan Mudianta; Victoria L Challinor; Anne E Winters; Karen L Cheney; James J De Voss; Mary J Garson

doi:10.3762/bjoc.9.329

Synthesis and determination of the absolute configuration of (-)-(5R,6Z)-dendrolasin-5-acetate from the nudibranch Hypselodoris jacksoni

Beilstein J Org Chem. 2013 Dec 23:9:2925-33. doi: 10.3762/bjoc.9.329.

Authors

I Wayan Mudianta¹, Victoria L Challinor¹, Anne E Winters², Karen L Cheney², James J De Voss¹, Mary J Garson¹

Affiliations

¹ School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane QLD 4072, Australia.
² School of Biological Sciences, The University of Queensland, Brisbane QLD 4072, Australia.

Abstract

A small sample of (-)-(5R,6Z)-dendrolasin-5-acetate, which was fully characterized by 2D NMR studies, was isolated from the nudibranch Hypselodoris jacksoni, along with the sesquiterpenes (+)-agassizin, (-)-furodysinin, (-)-euryfuran, (-)-dehydroherbadysidolide and (+)-pallescensone. A synthetic sample ([α]D -8.7) of the new metabolite was prepared by [1,2]-Wittig rearrangement of a geranylfuryl ether followed by acetylation of purified alcohol isomers. The absolute configuration at C-5 was established as R by the analysis of MPA ester derivatives of (Z)-5-hydroxydendrolasin obtained by preparative enantioselective HPLC.

Keywords: E/Z-isomers; Hypselodoris; enantioselective HPLC; natural products; nudibranch; sesquiterpene.