DFT calculations are performed to understand the conjugated N–N bond cleavage by Rh(<sc>iii</sc>)-catalyzed redox-neutral C–H activation of pyrazolones with PhCCPh.

Chiral α-functionalized α-amino ketones are sought-after compounds for drug development; however, their acyclic enantioselective synthesis with amines as nucleophiles remains challenging. The catalytic decarboxylation of propargylic cyclic carbonates through metal-allenylidene intermediates has proven to be an efficient route chiral quaternary centers, but its mechanisms require clarification. Herein, we computationally investigate the Cu(I)-catalyzed propargyl aniline [Guo, W. J. Am. Chem....

Spectroscopic studies on excited-state proton transfer of a new chromophore 2-(2′-benzofuryl)-3-hydroxychromone (BFHC) have been reported recently. In the present work, based time-dependent density functional theory (TD-DFT), intramolecular (ESIPT) BFHC is investigated theoretically. The calculated primary bond lengths and angles involved in hydrogen demonstrate that strengthened. addition, phenomenon reinforce has also testified infrared (IR) vibrational spectra as well bonding energies....

A mechanistic study of the Cp*RhIII-catalyzed C-H functionalization 2-acetyl-1-arythydrazines with diazo compounds in water was carried out by using density functional theory calculations. The results reveal that acetyl-bonded N-H deprotonation is prior to phenyl activation. mechanisms from protonation acetic acid disagree proposal Wang group. Different Rh(III)-catalyzed activation reported experimental literature, rate-determining step whole catalytic cycle an overall barrier 31.7 kcal...

The DFT mechanisms for Pd-catalyzed branching cyclizations of cross-conjugated enediyne-imides towards furo[2,3-<italic>b</italic>]pyridines have been investigated to discover the crucial factors controlling chemo- and solvent-directed product selectivity.

The mechanism of the cycloaddition reaction between singlet dichloroalkylidenesilylene and ethylene has been investigated with MP2/6-31G* B3LYP/6-31G* methods, including geometry optimization vibrational analysis for involved stationary points on potential energy surface. energies different conformations are calculated by CCSD(T)//MP2/6-31G* CCSD(T)//B3LYP/6-31G* methods. From surface profile obtained method ethylene, it can be predicted that dominant pathway this involves initial formation...

The mechanism of a cycloaddition reaction between singlet methylidenesilene and ethylene has been investigated with MP2/6-31G∗︁ B3LYP/6-31G∗︁ methods, including geometry optimization vibrational analysis for the involved stationary points on potential energy surface. Energies conformers were calculated by CCSD(T)//MP2/6-31G∗︁ CCSD(T)//B3LYP/6-31G∗︁ respectively. results show that dominant pathway is complex intermediate firstly formed two reactants through barrier-free exothermic 13.3...

The detailed mechanisms of the efficient <TEX>$\small{L}$</TEX>-proline and pyrrolidine catalyzed transamidation acetamide with benzylamine have been investigated using density functional theory (DFT) calculations. Our calculated results show: (1) two catalytic cycle reactions are similar. However, rate-determining steps their different for whole process. One is intramolecular nucleophilic addition reaction 1-COM, other hydrolysis 2-C. (2) COOH group essential transamidation. computational...

Abstract The mechanism of cycloaddition reaction between singlet alkylidene carbene and ethylene has been investigated with second‐order Moller‐Plesset perturbation theory (MP2). By using 6–31G* basis, geometry optimization, vibrational analysis energetics have calculated for the involved stationary points on potential energy surface. results show that title two major competition channels. An energy‐rich intermediate (INT) is firstly formed through a barrier‐free exothermic 63.62 kJ/mol,...

The Ni-catalyzed reactions of benzamides with bicyclic alkenes were explored using DFT calculations. An unprecedented "N-H deprotonation circumvented" catalytic mechanism was proposed, over the more common N-H/C-H activation mechanism, in which (i) circumvention N-H ensures presence N-H⋯O hydrogen bond interaction, thereby stabilizing critical ortho-C-H functionalization TS; and (ii) moiety retention results a weak N⋯Ni σ-coordination, is flexible to configurational conversion during key...

Abstract The mechanism of a cycloaddition reaction between singlet alkylidenestannylene and ethylene has been investigated with MP2/3‐21G* B3LYP/3‐21G* methods, including geometry optimization vibrational analysis for the involved stationary points on potential energy surface. Energies conformations were calculated by CCSD(T)//MP2/3‐21G* CCSD(T)//B3LYP/3‐21G* respectively. results show that dominant pathway is an intermediate (INT) firstly formed two reactants through barrier‐free exothermic...

Density functional theory (DFT) calculations have been performed to reveal the mechanism of gold(i)-catalyzed annulation N-allylynamides and benzofuroxans as nitrene transfer reagents construct azaheterocyclic compounds. The calculated results revealed that reaction mainly undergoes eight processes. Among steps, intramolecular nucleophilic attack imino N atom on α-position activated gold keteniminium is a rate-determining process, which different from proposed previously by experiment....