Insight into the organocatalytic arylation of azonaphthalenes with α-chloroaldehydes: the general mechanism and origin of selectivities

Abstract

A systemically computational study was performed to explore mechanism and origin of selectivities on organocatalytic arylation of azonaphthalenes with α-chloroaldehydes. The calculated results reveal that nucleophilicity of active sites and...

N‐Heterocyclic Carbene‐Catalyzed Asymmetric C−O Bond Construction Between Benzoic Acid and o‐Phthalaldehyde: Mechanism and Origin of Stereoselectivity

“…All the energies discussed below are based on the sum of the single‐point energies of 6‐311++G(2df, 2pd) and the Gibbs free energy corrections obtained by 6‐31G(d, p). As is well known, DFT has a wide range of applications in the mechanistic studies, such as organocatalytic reactions, [13a,c,17] transition‐metal catalyzed reactions, [18] enzyme reactions [19] and so on [20] . In addition, all the optimized structures of transition states, intermediates, reactants, and products were visualized by using CYLview [21] .…”

A (TD-)DFT study on photo-NHC catalysis: photoenolization/Diels–Alder reaction of acid fluorides catalyzed by N-heterocyclic carbenes

“…47–49 In this regard, we sought to explore the mechanistic features of the NHC-catalysed PEDA reaction in a comprehensive DFT study. 12–21,31–35 This investigation would provide insight into the central principles of photo-NHC catalysis by revealing the influence of the NHC catalyst on the absorption properties and excited state characteristics of the carbonyl function during the cycle. To the best of our knowledge, the excited state properties of acyl azolium species have not been studied in the context of organocatalysis and the degree to which their photochemistry resembles that of structurally related benzophenones has not been explored.…”

“…[1][2][3][4][5][6][7][8][9][10][11] In the last decade, much effort has been devoted to extending the scope of NHC organocatalysis beyond thermal two-electron processes. [12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] In this context, its combination with photochemical activation is a promising strategy to access new, complementary reaction modes that harness the distinct reactivity exhibited by open-shell species. [27][28][29][30] Most advances, however, have focused primarily on the combination with photoredox catalysis, leveraging an NHC's ability to act as a radical stabilizer and modulator of redox potentials thus promoting single-electron transfer events.…”

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

“…We believe that this work can systematically solve the above questions based on our previous research experience. [33][34][35][36][37][38][39][40][41][42][43][44] Due to the reliability of density functional theory (DFT) 45 in the study of the mechanism of organocatalytic and transition metal catalytic reactions, M06-2X 46 in conjunction with the standard 6-31G(d,p) basis set was employed for all geometry optimizations. The solvent effect was considered using the implicit SMD model, and N,N-dimethylformamide 47 was the reaction solvent used in calculations.…”