Bridging Amines with CO₂: Organocatalyzed Reduction of CO₂ to Aminals

The four-electron reduction of CO₂ in the presence of secondary aromatic amines is described for the first time to access aminals. Under metal-free hydrosilylation conditions, the four C–O bonds of CO₂ are cleaved, and the organocatalysts are able to balance the reactivity of CO₂ to promote the selective formation of two C–N and two C–H bonds. The methodology enables the formation of various symmetrical and unsymmetrical aminals