Concerted C-N/C-H Bond Formation in Highly Enantioselective Yttrium(III)-Catalyzed Hydroamination

A highly active oxazolinylborato yttrium hydroamination catalyst provides 2-methyl-pyrrolidines with excellent optical purities. The proposed mechanism, in which a yttrium(amidoalkene)amine complex reacts by concerted C-N and C-H bond formation, is supported by the rate law for conversion, substrate saturation under initial rates conditions, kinetic isotope effects, and isotopic perturbation of enantioselectivity. These features are conserved between oxazolinylborato Mg-, Y-, and Zr-mediated aminoalkene cyclizations, suggesting related transition states for all three systems. However, inversion of the products' absolute configuration between yttrium and zirconium catalysts coordinated by the same 4S-oxazolinylborate ligands highlight dissimilar mechanisms of stereoinduction.