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

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

  • Heift D Department of Chemistry and Applied Biosciences , ETH Zurich , CH-8093 Zurich , Switzerland . Email: hgruetzmacher@ethz.ch ; Email: zbenko@mail.bme.hu.
  • Benkő Z Department of Chemistry and Applied Biosciences , ETH Zurich , CH-8093 Zurich , Switzerland . Email: hgruetzmacher@ethz.ch ; Email: zbenko@mail.bme.hu.
  • Suter R Department of Chemistry and Applied Biosciences , ETH Zurich , CH-8093 Zurich , Switzerland . Email: hgruetzmacher@ethz.ch ; Email: zbenko@mail.bme.hu.
  • Verel R Department of Chemistry and Applied Biosciences , ETH Zurich , CH-8093 Zurich , Switzerland . Email: hgruetzmacher@ethz.ch ; Email: zbenko@mail.bme.hu.
  • Grützmacher H Department of Chemistry and Applied Biosciences , ETH Zurich , CH-8093 Zurich , Switzerland . Email: hgruetzmacher@ethz.ch ; Email: zbenko@mail.bme.hu.
  • 2018-07-24
Published in:
  • Chemical science. - 2016
English 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.
Language
  • English
Open access status
gold
Identifiers
Persistent URL
https://susi.usi.ch/global/documents/99682
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