Cookies

We use cookies to ensure that we give you the best experience on our website. You can change your cookie settings at any time. Otherwise, we'll assume you're OK to continue.

Department of Chemistry

Publication details for Dr Dominikus Heift

Heift, Dominikus, Benkő, Zoltán, Suter, Riccardo, Verel, René & Grützmacher, Hansjörg (2016). The reactivity of acyl chlorides towards sodium phosphaethynolate, Na(OCP): a mechanistic case study. Chemical Science 7(9): 6125-6131.

Author(s) from Durham

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.