Phosphine-Catalyzed Z-Selective Carbofluorination of Alkynoates Bearing an N-Heteroarene Unit

Abstract

We report herein on the phosphine-catalyzed Z-selective carbofluorination of alkynoates bearing an N-heteroarene unit, by using acyl fluorides as bifunctional reagents. This reaction proceeds through a pentacoordinate fluorophosphorane(V) intermediate, resulting in the formation of a C–F bond by a ligand coupling process. The Z-selectivity is attributed to the thermodynamic stabilization of a Z-isomer by orbital interactions between lone pair electrons of an N-heteroarene and the π* orbital of a carbonyl group.

Key words

phosphine redox catalysis - fluorophosphorane - carbofluorination - monofluoroalkene - n→π* interaction

Publication History

Received: 27 July 2022

Accepted: 21 September 2022

Accepted Manuscript online:
21 September 2022

Article published online:
27 October 2022

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