A DFT study on the mechanism and regioselectivity of NHC-catalyzed double acylation of aromatic 1,2-diketones with α,β-unsaturated ketones

Abstract

The possible mechanisms and origin of regioselectivity of N-heterocyclic carbene (NHC)-catalyzed double acylation reaction of aromatic 1,2-diketones with α,β-unsaturated ketones have been theoretically studied by density functional theory. Two regioselective...

Mechanism and Origin of Stereoselectivity of N-Heterocyclic Carbene (NHC)-Catalyzed Transformation Reaction of Benzaldehyde with o-QDM as Key Intermediate: A DFT Study

“…It is also a crucial but usually challenging issue to figure out how the catalyst will first exert its effect on reactants for a catalytic reaction. The answers would be different because various factors such as the specific structures of the catalyst, the reactant counterparts, and the experimental conditions are important. − Thus, we have also considered another competitive pathway that the NHC catalyst nucleophilically attacks the carbonyl atom of ketone to initiate the reaction. As shown in Figure S5, the energy barriers of Re / Si -TS1 ′ are 5.2/8.6 kcal/mol, which is lower than Re/Si -TS1 .…”

NHC-catalyzed enantioselective radical reactions of enal and pyridinium salt: mechanism and origin of regio- and stereoselectivities

“…In the present study, all computations were carried out using the Gaussian 16 program. 35 Due to the reliability of density functional theory in the mechanistic studies of organocatalytic reactions, [36][37][38][39][40][41][42][43] enzyme catalyzed reactions 44 and transition metal-catalyzed reactions, [45][46][47][48][49][50]…”

“…In the present study, all computations were carried out using the Gaussian 16 program. 35 Due to the reliability of density functional theory in the mechanistic studies of organocatalytic reactions, 36–43 enzyme catalyzed reactions 44 and transition metal-catalyzed reactions, 45–50 we have performed DFT calculations at the M06-2X (ref. 51 and 52)/6-311++G(d,p)/IEF-PCM HFB (ref.…”