Aminocatalysis has attracted attention as a catalytic method in large part due to the high stereoselectivity that can be achieved. This is typically attributed to the difference in activation energy of the diastereomeric transition states in the addition step. However, little attention has been paid to the roles and the relative stabilities of intermediates that lie downstream of the addition step. Recent mechanistic work and reports of unexplained selectivity patterns suggest that downstream intermediates may play a significant role in determining stereoselectivity. Herein, we present our DFT studies on the reaction pathway of γ-amination mediated by dienamine activation and comparing it with the enamine mediated α-amination. This work provides insight into the impact of the downstream intermediates in directing the stereochemical outcome of these enentioselective reactions.