Unprecedented Activation of CO 2 by α-Amino Boronic Acids.

Efficient and environmentally benign transformation of carbon dioxide (CO 2 ) into valuable chemicals is mainly obstructed by the lack of suitable catalysts. To date, various catalysts have already been investigated for the conversion of CO 2 molecules, but still finding metal-free, simple, and environment-friendly catalysts is a topic of utmost interest among researchers. Thus, in this regard, the present work projects α-amino boronic acids (AABs) as a metal-free and simple catalyst for CO 2 activation. The density functional theory (DFT)-based calculations have been carried out to explore the catalytic potential of AABs. The detailed electronic structure analysis of the considered AABs unveils the catalytic similarities with frustrated Lewis pairs (FLPs) in a gas phase. Interestingly, a peculiar catalytic action of AABs has been observed in the presence of solvents. The contrasting catalytic behavior of AABs in solvents has been extensively investigated by employing principal interacting orbital (PIO), intrinsic bond orbital (IBO), and natural bond orbital (NBO) analyses along the reaction paths. The results of the orbital studies provide concrete ground for the observed reaction mechanism. Further, the energetic analysis of the reaction of CO 2 with AABs reveals that <5 kcal/mol energy is required for activation in a solvent phase, and the formed adducts are readily active. These observations show that AABs can be considered as an efficient catalyst for CO 2 activation.