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

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. 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.