Heterogeneous Photocatalytic Ring Expansion of Cyclic Ketones for the Construction of Medium-Sized Lactams

J Org Chem. 2024 Mar 15;89(6):4031-4036. doi: 10.1021/acs.joc.3c02899. Epub 2024 Mar 6.

Abstract

Construction of medium-sized ring compounds remains challenging in synthetic chemistry. Herein, we describe the synthesis of medium-sized lactams via a photoinduced ring expansion of benzo-fused cyclic ketones using graphitic carbon nitride (g-C3N4) as a photocatalyst. The ring expansion protocol provided an efficient access to 8-10-membered lactams in good yields and displayed good tolerance to a range of functional groups. The mechanism studies revealed that the photochemical reaction proceeds via an intermediary of a nitrogen radical, which is generated through an oxidative hydrogen atom transfer (HAT) process.