Dr Dominikus Heift dominikus.heift@durham.ac.uk
Academic Visitor
The reactivity of acyl chlorides towards sodium phosphaethynolate, Na(OCP): a mechanistic case study
Heift, Dominikus; Benkő, Zoltán; Suter, Riccardo; Verel, René; Grützmacher, Hansjörg
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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http://creativecommons.org/licenses/by/4.0/
Copyright Statement
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
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