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

Open access
Date
2016-09-01Type
- Journal Article
Citations
Cited 21 times in
Web of Science
Cited 22 times in
Scopus
ETH Bibliography
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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. Show more
Permanent link
https://doi.org/10.3929/ethz-b-000119802Publication status
publishedExternal links
Journal / series
Chemical ScienceVolume
Pages / Article No.
Publisher
Royal Society of ChemistryOrganisational unit
03447 - Grützmacher, Hansjörg / Grützmacher, Hansjörg
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Citations
Cited 21 times in
Web of Science
Cited 22 times in
Scopus
ETH Bibliography
yes
Altmetrics