63. Mechanism, bonding nature of metal-nitrenoid, and selectivity for a nitrene-participating three-component carboamination of dienes: A DFT study

Chu, Y.; Bi S.;* Wu, X.; Jiang, Y.; Liu, Y.; Ling, B.; Yuan, A.  Mol. Catal. 2020, 497, 111222. Download Link

Abstract: A theoretical and computational study was performed on the nitrene-participating three-component carboamination of dienes. The reaction proceeds mainly through C–H activation, olefin insertion, metal nitrenoid formation, and selective C–N coupling. The role of solvent effect enables the extrusion of carbon dioxide to generate the key metal nitrenoid being not concerted but stepwise. The Rh = N was indicated by HOMO-LUMO interactions that the backdonation is dominant and hence showing the electron withdrawing behavior of nitrene. Regioselectivity for C–C bond formation, E-type product, and 1,4-carboamination was discussed.