Issue 12, 2019

Synthesis of acyl(chloro)phosphines enabled by phosphinidene transfer


Acyl(chloro)phosphines RC(O)P(Cl)(t-Bu) have been prepared by formal insertion of tert-butyl phosphinidene (t-Bu–P) from t-BuPA (A = C14H10 or anthracene) into the C–Cl bond of acyl chlorides. We show that the under-explored acyl(chloro)phosphine functional group provides an efficient method to prepare bis(acyl)phosphines, which are important precursors to compounds used industrially as radical polymerization initiators. Experimental and computational investigations into the mechanism of formation of acyl(chloro)phosphines by our synthetic method reveal a pathway in which chloride attacks a phosphonium intermediate and leads to the reductive loss of anthracene from the phosphorus center in a P(V) to P(III) process. The synthetic applicability of the acyl(chloro)phosphine functional group has been demonstrated by reduction to an acylphosphide anion, which can in turn be treated with an acyl chloride to furnish dissymmetric bis(acyl)phosphines.

Graphical abstract: Synthesis of acyl(chloro)phosphines enabled by phosphinidene transfer

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Article information

Article type
Edge Article
18 Dec 2018
06 Feb 2019
First published
07 Feb 2019
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2019,10, 3627-3631

Synthesis of acyl(chloro)phosphines enabled by phosphinidene transfer

K. M. Szkop, M. B. Geeson, D. W. Stephan and C. C. Cummins, Chem. Sci., 2019, 10, 3627 DOI: 10.1039/C8SC05657A

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