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Density functional theory (DFT) calculations were performed to investigate the mechanism and the enantioselectivity of the aza-Henry reaction of isatin-derived ketimine catalyzed by chiral guanidine-amide catalysts at the M06-2X-D3/6-311+G(d,p)//M06-2X-D3/6-31G(d,p) (toluene, SMD) theoretical level. The catalytic reaction occurred via a three-step mechanism: (i) the deprotonation of nitromethane by a chiral guanidine-amide catalyst; (ii) formation of C-C bonds; (iii) H-transfer from guanidine to ketimine, accompanied with the regeneration of the catalyst. A dual activation model was proposed, in which the protonated guanidine activated the nitronate, and the amide moiety simultaneously interacted with the ketimine substrate by intermolecular hydrogen bonding. The repulsion of CPh 3 group in guanidine as well as N -Boc group in ketimine raised the Pauli repulsion energy (∆ E  Pauli ) and the strain energy (∆ E  strain ) of reacting species in the unfavorable si -face pathway, contributing to a high level of stereoselectivity. A new catalyst with cyclopropenimine and 1,2-diphenylethylcarbamoyl as well as sulfonamide substituent was designed. The strong basicity of cyclopropenimine moiety accelerated the activation of CH 3 NO 2 by decreasing the energy barrier in the deprotonation step. The repulsion between the N -Boc group in ketimine and cyclohexyl group as well as chiral backbone in the new catalyst raised the energy barrier in C-C bond formation along the si -face attack pathway, leading to the formation of R -configuration product. A possible synthetic route for the new catalyst is also suggested.

Guanidine–Amide-Catalyzed Aza-Henry Reaction of Isatin-Derived Ketimines: Origin of Selectivity and New Catalyst Design