Issue 9, 2016

The reactivity of acyl chlorides towards sodium phosphaethynolate, Na(OCP): a mechanistic case study

Abstract

The reaction of Na(OCP) with mesitoyl chloride delivers an ester functionalized 1,2,4-oxadiphosphole in a clean and P-atom economic way. The reaction mechanism has been elucidated by means of detailed NMR-spectroscopic, kinetic and computational studies. The initially formed acyl phosphaketene undergoes a pseudo-coarctate cyclization with an (OCP) anion under the loss of carbon monoxide to yield a five-membered ring anion. Subsequently, the nucleophilic attack of the formed heterocyclic anion on a second acyl chloride molecule results in the 1,2,4-oxadiphosphole. The transient acyl phosphaketene is conserved during the reaction in the form of four-membered ring adducts, which act as a reservoir. Consequently, the phosphaethynolate anion has three different functions in these reactions: it acts as a nucleophile, as an en-component in [2 + 2] cycloadditions and as a formal P transfer reagent.

Graphical abstract: The reactivity of acyl chlorides towards sodium phosphaethynolate, Na(OCP): a mechanistic case study

Supplementary files

Article information

Article type
Edge Article
Submitted
21 Mar 2016
Accepted
30 May 2016
First published
17 Jun 2016
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., 2016,7, 6125-6131

The reactivity of acyl chlorides towards sodium phosphaethynolate, Na(OCP): a mechanistic case study

D. Heift, Z. Benkő, R. Suter, R. Verel and H. Grützmacher, Chem. Sci., 2016, 7, 6125 DOI: 10.1039/C6SC01269H

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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