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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.

SUBMITTER: Heift D

PROVIDER: S-EPMC6024182 | biostudies-literature | 2016 Sep

REPOSITORIES: biostudies-literature

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

Heift Dominikus D Benkő Zoltán Z Suter Riccardo R Verel René R Grützmacher Hansjörg H

Chemical science 20160617 9

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 heterocyc ...[more]

PMID: 30034752

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