A Catalytic Oxidative Quinone Heterofunctionalization Method: Synthesis of Strongylophorine‐26

The preparation of heteroatom‐substituted p ‐quinones is ideally performed by direct addition of a nucleophile followed by in situ reoxidation. Albeit an appealing strategy, the reactivity of the p ‐quinone moiety is not easily tamed and no broadly applicable method for heteroatom functionalization exists. Shown herein is that Co(OAc) 2 and Mn(OAc) 3 ⋅2 H 2 O act as powerful catalysts for oxidative p ‐quinone functionalization with a collection of O, N, and S nucleophiles, using oxygen as the terminal oxidant. Preliminary mechanistic observations and the first synthesis of the cytotoxic natural product strongylophorine‐26 is presented.