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

Fıstıkçı M.

Journal of Physical Organic Chemistry, vol.35, no.10, 2022 (SCI-Expanded) identifier

  • Publication Type: Article / Article
  • Volume: 35 Issue: 10
  • Publication Date: 2022
  • Doi Number: 10.1002/poc.4398
  • Journal Name: Journal of Physical Organic Chemistry
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Academic Search Premier, Applied Science & Technology Source, Chemical Abstracts Core, Compendex, INSPEC
  • Keywords: DFT, hydrogen atom transfer (HAT), thioalkyne, trifluoromethylation
  • Hakkari University Affiliated: Yes


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.