Photooxygenation of a Microbial Arene Oxidation Product and Regioselective Kornblum–DeLaMare Rearrangement: Total Synthesis of Zeylenols and Zeylenones

Abstract

We report the enantioselective total syntheses of zeylenol (+)-1, as well as its congeners (-)-7 and 16, and of 3-O-debenzoylzeylenone 28. To this end, a new variant of the Kornblum-DeLaMare rearrangement, which utilises neighbouring-group participation to impart regioselectivity, has been developed. The approach employs photooxygenation of building blocks derived from a microbial arene oxidation product.