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

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.