Bioinspired Synthesis of a Sedaxane Metabolite Using Catalytic Vanadyl Acetylacetonate and Molecular Oxygen

摘要

A bioinspired synthesis of the sedaxane metabolite 2 from intermediate 3 using catalytic VO(acac)(2) and O-2 is described. Intermediate 3 was synthesized starting from 2-bromostyrene in four steps. The inner cyclopropyl ring of 3 was assembled with trans geometry using a highly diastereoselective Nishiyama cydopropanation, and the outer hydroxycyclopropyl ring was installed using the Kulinkovich cyclopropanation. Additionally, conversion of 3 into 2 was demonstrated in in vitro microbial culture experiments consisting of bacteria and fungi.