Total synthesis and stereochemical assignment of bipolamide A acetate.

Abstract

Asymmetric total synthesis of an acetate analogue of the endophytic unstable secondary metabolite bipolamide A has been achieved for the first time adopting a convergent approach. The key feature of this synthesis includes Evans's asymmetric ethylation, Wittig olefination, Takai olefination, stereoselective Grignard addition and intermolecular Heck coupling. This eventually developed a synthetic route of the rarely found branched amine bearing an acyloin moiety. Our synthesis finally established unambiguously the stereochemistry of the unassigned C-8 center of the naturally occurring unstable bipolamide A.