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

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Eşsiz S.

RSC Advances, cilt.11, sa.30, ss.18246-18251, 2021 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 11 Sayı: 30
  • Basım Tarihi: 2021
  • Doi Numarası: 10.1039/d1ra01649k
  • Dergi Adı: RSC Advances
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Biotechnology Research Abstracts, Chemical Abstracts Core, Compendex, Metadex, Directory of Open Access Journals
  • Sayfa Sayıları: ss.18246-18251
  • Hakkari Üniversitesi Adresli: Evet

Özet

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