Heift, Dominikus, Benkő, Zoltán, Suter, Riccardo, Verel, René and Grützmacher, Hansjörg (2016) The reactivity of acyl chlorides towards sodium phosphaethynolate, Na(OCP) : a mechanistic case study. Chemical Science, 7(9), pp. 6125-6131. ISSN (print) 2041-6520
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.
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