A Photochemical Strategy for the Synthesis of Caprolactams via Dearomative Ring-Expansion of Nitroarenes

Abstract

This paper outlines a novel strategy for the preparation of seven-membered ring lactams from simple nitroarenes. The approach is based on a photochemical dearomative ring expansion starting with the conversion of the nitro group into a singlet nitrene. This process is mediated by blue light, occurs at room temperature and overall enables the insertion of the nitro N-atom into the benzenoid framework. This step transforms the aromatic starting material into a seven-membered ring azepine, that, following hydrogenation and hydrolysis, is converted into the desired caprolactams in just three steps.