The reactivity of acyl chlorides towards sodium phosphaethynolate, Na(OCP): a mechanistic case study. Issue 9 (17th June 2016)

• Record Type: Journal Article
• Authors: Heift, Dominikus; Benkő, Zoltán; Suter, Riccardo; Verel, René; Grützmacher, Hansjörg
• Is Part Of: Chemical science. Volume 7:Issue 9(2016:Sep.)
• Page Start: 6125
• Page End: 6131
• Publication Date: 2016-06-17
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c6sc01269h
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : The phosphaethynolate anion (OCP) − has three different functions in the reaction with 2, 4, 6-trimethylbenzoyl chloride (MesCOCl): it acts as a nucleophile, as an en-component in [2 + 2] cycloadditions and as a formal P − transfer reagent. 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.