Direct ortho-C-H functionalization of aromatic alcohols masked by acetone oxime ether via exo-palladacycle.

A simple and practical exo-oxime ether auxilixary for ortho-C-H functionalization of aromatic alcohols has been developed. Selective olefination of aromatic alcohols were first achieved via a six- or seven-membered exo-acetone oxime ether palladacycle with broad substrate scope. In addition, the crystal of the exo-palladacycle intermediate was obtained for the first time, and the application of this method in total synthesis of 3-deoxyisoochracinic acid was accomplished via a novel retro-synthetic disconnection approach, thus demonstrating the utility of this transformation.