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Theoretical Study of the Mechanism of Catalytic Enanteoselective N-H and O-H Insertion Reactions.

Theoretical Density Functional Theory (DFT) calculations were carried out to study bond insertion reactions using a copper (I) carbenoid with (S,S)-2,2-Bis(4-phenyl-2-oxazolin-2-yl) ligand as a bond activator. In order to understand the reaction mechanism where N-H and O-H bonds actively participate, the reaction force (RF) and activation strain model (ASM) were used. Results indicate that the first step of the reaction is barrierless for both bond insertions (N-H and O-H), and the second step of the insertion reaction in the phenol (O-H bond) is favored kinetically and thermodynamically with regards to the aniline substrate (N-H bond). The enantioselectivity is driven by the ligand of the catalyst by steric repulsion, favoring the formation of the R isomer. The analysis of the Reaction Force and ASM exhibited that the higher energy barrier in aniline is mainly due to a higher W2 contribution together with repulsive interaction, which hinders the insertion process.