Exploiting the radical reactivity of diazaphosphinanes in hydrodehalogenations and cascade cyclizations.

Chemical Science
Jingjing ZhangJin-Pei Cheng

Abstract

The remarkable reducibility of diazaphosphinanes has been extensively applied in various hydrogenations, based on and yet limited by their well-known hydridic reactivity. Here we exploited their unprecedented radical reactivity to implement hydrodehalogenations and cascade cyclizations originally inaccessible by hydride transfer. These reactions feature a broad substrate scope, high efficiency and simplicity of manipulation. Mechanistic studies suggested a radical chain process in which a phosphinyl radical is generated in a catalytic cycle via hydrogen-atom transfer from diazaphosphinanes. The radical reactivity of diazaphosphinanes disclosed here differs from their well-established hydridic reactivity, and hence, opens a new avenue for diazaphosphinane applications in organic syntheses.

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Citations

Oct 21, 2020·Chemical Society Reviews·Alexander W H Speed
Aug 13, 2021·Physical Chemistry Chemical Physics : PCCP·Mohammed F AlkhaterCharles B Musgrave

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