Diamine Catalyzed Addition of ZnEt2 to PhC(O)CF3: Two Mechanisms and Autocatalytic Asymmetric Enhancement

Abstract

NMR studies of the catalytic addition reaction of ZnEt2 to PhC(O)CF3 in the presence of three very efficient catalysts [TMEDA, tBuBOX, and L; where L is a chiral diamine synthesized from optically pure (R,R)-1,2-diphenylethylenediamine and (S)-2,2'-bis-(bromomethyl)-1,1'-binaphthalene] reveal large differences in their behavior. For the ligands TMEDA and tBuBOX, the catalysis shows no unusual features and proceeds via [(N?N)Zn(Et){OC(CF3 )(Et)Ph}]. For N?N?L, the observation of autocatalytic asymmetric enhancement during the catalysis, and unusual inverse concentration dependence on the reaction rate, indicate the participation of an additional novel catalytic cycle that goes through a dinuclear intermediate containing one ZnEt2 and one ZnEt fragment connected by N?N and OR bridges. Interestingly, the (19) F NMR signals of the main product of the reaction ([Zn(Et){OC*(CF3 )(Et)Ph}]2 ) allowed us to assess the enantioselectivity of the processes in situ without the assistance of chiral chromatography.