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.