Direct Metal-Free Transformation of Alkynes to Nitriles: Computational Evidence for the Precise Reaction Mechanism.

ABSTRACT: Density functional theory calculations elucidated the precise reaction mechanism for the conversion of diphenylacetylenes into benzonitriles involving the cleavage of the triple C≡C bond, with N-iodosuccinimide (NIS) as an oxidant and trimethylsilyl azide (TMSN₃) as a nitrogen donor. The reaction requires six steps with the activation barrier ΔG^‡ = 33.5 kcal mol^-1 and a highly exergonic reaction free-energy ΔG_R = -191.9 kcal mol^-1 in MeCN. Reaction profiles agree with several experimental observations, offering evidence for the formation of molecular I₂, interpreting the necessity to increase the temperature to finalize the reaction, and revealing thermodynamic aspects allowing higher yields for alkynes

SUBMITTER: Hok L 

PROVIDER: S-EPMC8004279 | biostudies-literature | 2021 Mar

REPOSITORIES: biostudies-literature