Publication details for Dr Dominikus HeiftHeift, 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.
- Publication type: Journal Article
- ISSN/ISBN: 2041-6520 (print), 2041-6539 (electronic)
- DOI: 10.1039/C6SC01269H
- Further publication details on publisher web site
- Durham Research Online (DRO) - may include full text
Author(s) from Durham
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.