Photocatalyst-free, visible-light-induced regio- and stereoselective synthesis of phosphorylated enamines from N-allenamides via [1,3]-sulfonyl shift at room temperature

Abstract

Herein, we report the first visible-light-induced strategy for the rapid synthesis of densely functionalized α- and γ-phosphorylated β-sulfonyl enamines in a regio- and stereoselective manner from N-sulfonyl allenamides and H-phosphine oxides. The transformation displays a broad substrate scope, while operating at room temperature under photocatalyst- and additive-free conditions. In this atom-economical process, either terminal or substituted N-sulfonyl allenamides trigger an unprecedented N-to-C [1,3]-sulfonyl shift, relying on a dual radical allyl resonance and α-heteroatom effect in its triplet excited state. A plausible reaction mechanism is proposed which was supported by the outcomes of theoretical approaches based on Density Functional Theory (DFT) calculations.