Exploiting the radical reactivity of diazaphosphinanes in hydrodehalogenations and cascade cyclizations

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.