N-Oxide-to-Carbon Transmutations of Azaarene N-Oxides.

Reactions that change the identity of an atom within a ring system are emerging as valuable tools for the site-selective editing of molecular structures. Herein, we describe the expansion of an underdeveloped transformation that directly converts azaarene-derived N-oxides to all-carbon arenes. This ring transmutation exhibits good functional group tolerance and replaces the N-oxide moiety with either unsubstituted, substituted, or isotopically labeled carbon atoms in a single laboratory operation.

A C-H Functionalization Strategy Enables an Enantioselective Formal Synthesis of (-)-Aflatoxin B2.

An enantioselective formal synthesis of (-)-aflatoxin B2 from 4-methoxyphenylacetic acid has been achieved by an approach that produces a key carbon-carbon bond, a benzylic stereocenter, and two arene carbon-oxygen bonds in the course of three site-selective C-H functionalizations. The carbonyl-directed acetoxylation of two arene C-H bonds described herein is unprecedented in natural product synthesis and occurs under mild conditions that preserve the configuration of a sensitive benzylic stereocenter.