DFT investigation on the mechanisms of Csp-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 at the 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 Csp 3 -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 O 2 . The additive InCl 3 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 paths 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. The mechanism of Csp 3 -H functionalization between ethyl 2-( p -tolylamino)acetate and phenylethylene initiated by tris(4-bromophenyl)aminium hexachloroantimonate was elaborated based on DFT calculations.