Photoinduced direct C–H cyanoalkylation of azauracils via electron donor–acceptor complex activation

Abstract

Photoinduced C–H functionalization of azauracils predominantly relies on the use of noble metal photocatalysts or synthetically elaborated organic dyes to achieve selective reactivity. Herein, we report direct C–H cyanoalkylation of azauracils with cycloketone oxime esters via electron donor–acceptor (EDA) complex photoactivation. The transiently formed chromophoric assembly between azauracils and cycloketone oxime esters plays a pivotal role in enabling intermolecular electron transfer, thereby driving the C–H cyanoalkylation process. Mechanistic studies and density functional theory (DFT) calculations support the proposed EDA complex scenario. This synthetic approach operates under redox-neutral conditions without exogenous photocatalysts and additives, showcasing significant potential for drug design and bioactive molecule synthesis.