Ligand Control of Geometric Selectivity in Protosilylation of Acyclic α-Substituted α,β-Unsaturated <i>N</i>-Sulfinyl Ketimines

The copper(I)-catalyzed silyl conjugate addition to α-substituted α,β-unsaturated <i>N</i>-<i>tert</i>-butanesulfinyl ketimines presents a facile approach for the synthesis of acyclic β,β-disubstituted enesulfinamides. By varying the ligand associated with the copper catalysts, it is feasible to selectively produce multisubstituted enesulfinamides with either (<i>Z</i>)- or (<i>E</i>)-configuration, thereby facilitating their effective use in the stereoselective nucleophilic reactions to construct less accessible acyclic quaternary or tetrasubstituted stereocenters, encompassing both absolute configurations.