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

Heift, Dominikus; Benkő, Zoltán; Suter, Riccardo; Verel, René; Grützmacher, Hansjörg

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


Authors

Zoltán Benkő

Riccardo Suter

René Verel

Hansjörg Grützmacher



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.

Citation

Heift, D., Benkő, Z., Suter, R., Verel, R., & Grützmacher, H. (2016). The reactivity of acyl chlorides towards sodium phosphaethynolate, Na(OCP): a mechanistic case study. Chemical Science, 7(9), 6125-6131. https://doi.org/10.1039/c6sc01269h

Journal Article Type Article
Acceptance Date May 30, 2016
Online Publication Date Jun 17, 2016
Publication Date Sep 1, 2016
Deposit Date Feb 22, 2017
Publicly Available Date Mar 28, 2017
Journal Chemical Science
Print ISSN 2041-6520
Electronic ISSN 2041-6539
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 7
Issue 9
Pages 6125-6131
DOI https://doi.org/10.1039/c6sc01269h

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