Importance of additive effects on the reactivity of Ag catalyzed domino cyclization: a computational chemistry survey

Abstract

The mechanism and origins of selectivity in a silver-catalyzed domino cyclization to spiroindolines were explored using DFT investigations. It is exposed that both dearomatization with solvent and hydroamination are controlled by TFA via hydrogen bond interactions network that is revealed to play a key role in the successful realization of the silver-catalyzed domino cyclization. Most notably, our results demonstrated that the cooperation between TFA and AgOTf is of importance for the hydroamination step. This work provides a clear evidence of the ability to precisely control the selectivity on the asymmetric synthesis through the tuning of additive.