DFT Investigation for the Mechanisms of Csp3-H Functionalization of Glycine Derivatives Induced by Radical Cation Salt
The mechanisms for the reaction between ethyl 2-(p-tolylamino)acetate and phenylethylene have been investigated using M06-L-D3/6-311+G(d,p) level, and the SMD model was applied to simulate the solvent. The computational results suggest that the Csp3-H functionalization of ethyl 2-(p-tolylamino)acetate has two possible paths; then there are three probable paths (I, II or III) to yield the final product. In path I, one D-A addition reaction could produce the product compound; finally the oxidative dehydrogenation could yield the product with the assistance of O2. The additive InCl3 can accelerate the D-A reaction via four possible paths, and the NOFF, FMOT and Fukui function can be applied to analyze the D-A reaction; while in path II and III, the formed radical intermediate would go through a series of addition reaction, oxidation reaction, ring-closure reaction and oxidative dehydrogenation to yield the final product. The results could provide valuable insights into these types of interactions and related ones.