A computational study for the reaction mechanism of AIBN-induced remote trifluoromethyl-alkynylation of thioalkynes

Fıstıkçı M.

Journal of Physical Organic Chemistry, cilt.35, sa.10, 2022 (SCI-Expanded) identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 35 Sayı: 10
  • Basım Tarihi: 2022
  • Doi Numarası: 10.1002/poc.4398
  • Dergi Adı: Journal of Physical Organic Chemistry
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Academic Search Premier, Applied Science & Technology Source, Chemical Abstracts Core, Compendex, INSPEC
  • Anahtar Kelimeler: DFT, hydrogen atom transfer (HAT), thioalkyne, trifluoromethylation
  • Hakkari Üniversitesi Adresli: Evet

Özet

A computational study for 2,2-azobis (isobutyronitrile) (AIBN)-induced remote trifluoromethyl-alkynylation of thioalkynes is carried out employing the density functional theory (DFT). According to our computations, the decomposition of AIBN, which is the initial step of the radicalic reaction, include the highest reaction energy step and indicate that the rate-determining step is the decomposition of AIBN for the reaction scheme. Our computations show that the reaction can also proceed through the vinyl radicals 12 and 18 as well as the vinyl radicals 3 and 10 suggested by Zhu and co-workers. The computations are compatible with experimental data. Moreover, our computations provide useful insight into the radicalic mechanism of AIBN-induced remote trifluoromethyl-alkynylation of thioalkynes.