Metal-free highly chemo-selective bisphosphorylation and deoxyphosphorylation of carboxylic acids?

Chemical Science Pub Date: 2023-04-24 DOI: 10.1039/D3SC01148H

Abstract

Carboxylic acids are readily available in both the natural and synthetic world. Their direct utilization for preparing organophosphorus compounds would greatly benefit the development of organophosphorus chemistry. In this manuscript, we describe a novel and practical phosphorylating reaction under transition metal-free reaction conditions that can selectively convert carboxylic acids into the P–C–O–P motif-containing compounds through bisphosphorylation, and the benzyl phosphorus compounds through deoxyphosphorylation. This strategy provides a new route for carboxylic acid conversion as the alkyl source, enabling highly efficient and practical synthesis of the corresponding value-added organophosphorus compounds with high chemo-selectivity and wide substrate scope, including the late modification of complex APIs (active pharmaceutical ingredients). Moreover, this reaction also indicates a new strategy for converting carboxylic acids into alkenes by coupling this work and the subsequent WHE reaction with ketones and aldehydes. We anticipate that this new mode of transforming carboxylic acids will find wide application in chemical synthesis.

Graphical abstract: Metal-free highly chemo-selective bisphosphorylation and deoxyphosphorylation of carboxylic acids
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