CuCN and trimethylsilyl chloride-catalyzed regiospecific Grignard reactions to CF3-containing allylic derivatives

Article abstract of DOI:10.1002/ijch.199900025

CF₃-containing allylic alcohol derivatives were treated with an appropriate Grignard reagent in the presence of catalytic amounts of CuCN and trimethylsilyl chloride (TMSCl) to furnish products via the clean anti-S_N2′ mechanism. Experimental results as well as ab initio computational analyses unambiguously demonstrated the important roles of TMSCl as a Lewis basic additive for smooth promotion of reductive elimination and inhibition of the "Cu...F" climination leading to undesired byproduct formation.