Mechanistic Insight into the Cu-Catalyzed C-S Cross-Coupling of Thioacetate with Aryl Halides. A Joint Experimental-Computational Study

SILVIA SORIA CASTRO; DIEGO ANDRADA; CAMINOS, DANIEL A.; JUAN E. ARGÜELLO; MARC ROBERT; PEÑÉÑORY ALICIA B

JOURNAL OF ORGANIC CHEMISTRY

AMER CHEMICAL SOC

Lugar: Washington; Año: 2017 vol. 82 p. 11464 - 11464

0022-3263

he mechanism of the Ullmann-type reaction between potassium thioacetate (KSAc) and iodobenzene (PhI) catalyzed by CuI associated with 1,10-phenanthroline (phen) as a ligand has been explored experimentally and computationally. The study on C-S bond formation has been investigated by UV-visible spectrophotometry, cyclic voltammetry and products assessment from radical probes. The results indicate that under experimental conditions the catalytically active species is [(phen)Cu(SAc)]+ regarless the copper sources. An examination of the aryl halide activation mechanism using radical probes was undertaken. No evidences of the presence of radical species have been found during the reaction process, which is consistent with an oxidative addition cross coupling. The different reaction pathways leading to the experimentally observed reaction products have been studied by DFT calculation. The oxidative addition ? reductive elimination mechanism via an unstable CuIII intermediate is energeticall