A computational study for the reaction mechanism of metal-free cyanomethylation of aryl alkynoates with acetonitrile

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Eşsiz S.

RSC Advances, vol.11, no.30, pp.18246-18251, 2021 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 11 Issue: 30
  • Publication Date: 2021
  • Doi Number: 10.1039/d1ra01649k
  • Journal Name: RSC Advances
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Biotechnology Research Abstracts, Chemical Abstracts Core, Compendex, Metadex, Directory of Open Access Journals
  • Page Numbers: pp.18246-18251
  • Hakkari University Affiliated: Yes


A computational study of metal-free cyanomethylation and cyclization of aryl alkynoates with acetonitrile is carried out employing density functional theory and high-level coupled-cluster methods, such as coupled-cluster singles and doubles with perturbative triples [CCSD(T)]. Our results indicate that the reaction of aryl alkynoates with acetonitrile in the presence of tert-butyl peroxybenzoate (TBPB) under metal-free conditions tends to proceed through cyanomethylation, spirocyclization and ester migration of the kinetically favoured coumarin derivatives. 1,2-Ester migration in the spiro-radical intermediate 10 does not proceed via the formation of the carboxyl radical 11 suggested by Sun and co-workers. Our results also demonstrate that the t-butoxy radical is substantially responsible the formation of the cyanomethyl radical by the abstraction of a hydrogen atom from acetonitrile. This journal is