Chemical Science [SOPhy]

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 fashion from N-sulfonyl allenamides and H-phosphine oxides. The transformation displays a broad susbtrate, 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 outcomes of theoretical approaches rooted in Density Functional Theory (DFT) calculations.

Graphical Abstract:

 

 

Reference:

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

Jia-Dong Guo, Feven Alemu Korsaye, Dorian Schutz, Ilaria Ciofini and Laurence Miesch

Chem. Sci., 2024, (first published on 03 Oct 2024), DOI: https://doi.org/10.1039/D4SC05190D

Contact :

Laurence Miesch, équipe SOPhy, Institut de Chimie de Strasbourg (UMR 7177).