197657-90-2Relevant academic research and scientific papers
Highly stereoselective S(N)2' reactions of Grignard reagents towards CF3-containing allylic acetates
Yamazaki, Takashi,Umetani, Hideki,Kitazume, Tomoya
, p. 6705 - 6708 (1997)
γ-Trifluoromethylated allylic acetates were found to quite smoothly proceed S(N)2' type reaction with various Grignard reagents in the presence of a catalytic amount of CuCN and TMS-Cl, without any trace amount of the corresponding S(N)2 products in all cases examined due to the electronic effect of a CF3 group.
CuCN and trimethylsilyl chloride-catalyzed regiospecific Grignard reactions to CF3-containing allylic derivatives
Yamazaki, Takashi,Umetani, Hideki,Kitazume, Tomoya
, p. 193 - 205 (2007/10/03)
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-SN2′ 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.
