A DFT Study on the NHC-Catalyzed Reaction of Enals with Aminoacrylates: Mechanism, Regioselectivity, and Stereoselectivity DOI
Yan Li, Junjie Xiao,

Yanlong Kang

et al.

The Journal of Physical Chemistry A, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 27, 2024

DFT (M06-2X) calculations were used to study the NHC-catalyzed [3 + 3] cycloaddition of enals with aminoacrylates. The catalytic cycle begins binding NHC enal. Subsequent intramolecular proton transfer generates Breslow intermediate. This intermediate undergoes an oxidative reaction, leading formation acyl azolium intermediate, which further reacts other substrate aminoacrylate via a new C–C bond formation. step determines stereoselectivity current and re-face addition mode S-configuration is predominant. Afterward, sequential protonation, deprotonation, cyclization form six-membered cyclic upon elimination affords final product dihydropyridinone. computed enantiomeric excess (99.1% ee) in very good agreement experimentally reported value (99% ee). origin enantioselectivity traced stronger LP···π interactions between favored S-congurational transition state.

Language: Английский

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

Yilu Luo,

M. Zhao, Yang Wang

et al.

The Journal of Physical Chemistry A, Journal Year: 2024, Volume and Issue: 128(30), P. 6190 - 6198

Published: July 18, 2024

N-heterocyclic carbene (NHC)-bound

Language: Английский

Citations

5
Mechanistic studies on an isothiourea-catalyzed reaction of an aromatic ester with an imine DOI

Meng-Qing Yang,

Yang Wang

Molecular Catalysis, Journal Year: 2024, Volume and Issue: 567, P. 114445 - 114445

Published: Aug. 10, 2024

Language: Английский

Citations

4
Asymmetric construction of axial and planar chirality with N-heterocyclic carbene (NHC) organocatalysis DOI
Meng Zhang,

Xiaoqun Yang,

Xiaolin Peng

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 30, 2024

Language: Английский

Citations

4
Theoretical investigation on the reaction mechanism and origin of stereoselectivity of a three-component coupling reaction under organocatalysis DOI

Yujian Yu,

Lujun Zhang, Yang Wang

et al.

Molecular Catalysis, Journal Year: 2025, Volume and Issue: 573, P. 114819 - 114819

Published: Jan. 6, 2025

Language: Английский

Citations

0
Mechanisms of C(sp3)-H Functionalization of Acetonitrile or Acetone with Alkynes: A DFT Investigation DOI
Bin Chen,

Tiantian Feng,

Da‐Gang Zhou

et al.

Journal of Chemical Information and Modeling, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 6, 2025

The mechanisms for the C(sp3)-H activation and addition reactions between acetonitrile (or acetone) alkynes have been investigated with M06-2X-D3/ma-def2-TZVP method basis set. SMD (solvation model based on solute electron density) was applied to simulate solvent effect. In first second reactions, 2-phenylbut-3-yn-2-ol reacted acetone, respectively. First, activations of acetone could be achieved by PhCOO• t-BuO• radicals. Then, converted into final products P1 P2. Gibbs free energy surfaces these two suggest that blue lines would favorable paths lower barriers, terminal C atom C≡C bond is best reactive site. Moreover, analysis IRI (Interaction Region Indicator) reveals Z- E-configuration transformations. While in third fourth methyl(2-(phenylethynyl)phenyl)sulfane has interactions via some paths, profiles show C10 atom, rather than C11 priority, are favorable. Furthermore, action mode Na2HPO4 reduce barrier benefit reaction. vdW (van der Waals) play an important role choice fifth sixth) reaction, it happened 1-(2-(methylthio)phenyl)-3-phenylprop-2-yn-1-one acetontrile yield product P5 P6). computational results uncovered line path, site depends interactions, which origin selectivity. addition, investigation byproducts carried out, can explain reason only main produced. Both those agree experimental results. localized orbital locator (LOL) isosurfaces, Laplacian order (LBO), density critical point (ρBCP), spin isosurface graphs, graphs used analyze structure reveal reaction substances.

Language: Английский

Citations

0
Mechanism and Origins of Regio- and Stereoselectivities of NHC-Catalyzed Dearomative Annulation of Benzoazoles and Cinnamaldehydes from DFT DOI
Yan Li,

Yanlong Kang,

Junjie Xiao

et al.

The Journal of Physical Chemistry A, Journal Year: 2025, Volume and Issue: unknown

Published: March 5, 2025

A theoretical study on the mechanism, regioselectivity, and enantioselectivity of NHC-catalyzed dearomatizing annulation benzoxazoles with enals has been conducted using density functional theory calculations. Our calculated results indicate that favored mechanism occurs through eight reaction steps: initial binding NHC to enals, followed by formation Breslow intermediate via proton transfer. Subsequent oxidation generates α,β-unsaturated acylazolium intermediate, which can undergo Michael addition benzoxazoles. Sequential protonation/deprotonation/cyclization produces six-membered cyclic undergoes catalyst elimination, leading final product. DABCO·H+ was found play important roles in transfer cyclization. Without DABCO·H+, energy barrier up 44.2 kcal/mol for step 2 is too high be accessible. With corresponding value lowered 18.6 kcal/mol. The cyclization 7.4 DABCO·H+. determines both regioselectivity. According NCI analysis, controlled strong interactions (such as C-H···O, C-H···N, π···π) between We also discuss solvent substituent effects role NHC. mechanistic insights obtained present would help improving current systems or designing new synthetic routes.

Language: Английский

Citations

0
Chiral phosphoric acid (CPA)-catalyzed transformation reaction of ketene: Competing mechanisms and origin of regio- and stereoselectivities DOI
Han Zhang, Keyuan Zhao, Donghui Wei

et al.

Molecular Catalysis, Journal Year: 2024, Volume and Issue: 560, P. 114150 - 114150

Published: April 16, 2024

Language: Английский

Citations

3
Both N-F oxidant and NaF determined reaction yield in the organoselenium-catalyzed oxidative ring-closing reaction of unsaturated alcohol: A theoretical study DOI
Chao-Xian Yan,

Lei-Tao Wei,

Weiqin Gao

et al.

Molecular Catalysis, Journal Year: 2024, Volume and Issue: 567, P. 114442 - 114442

Published: Aug. 13, 2024

Language: Английский

Citations

2
Catalytic Asymmetric Reductive Amination for Axially Chiral Aryl Aldehydes via Desymmetrization/Kinetic Resolution Cascade DOI
Yi Wang,

Rui‐Ping Song,

Xinyue Li

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(34), P. 7161 - 7165

Published: Aug. 19, 2024

Herein we present an efficient chiral phosphoric-acid-catalyzed atropoenantioselective asymmetric reductive amination of biaryl dialdehydes. The process involves desymmetrization and the following kinetic resolution, with a wide range axially aryl aldehydes obtained high optical purities.

Language: Английский

Citations

1
DFT Study on the Mechanism of Phosphine-Catalyzed Ring-Opening Reaction of Cyclopropyl Ketone DOI
Xiaohan Yu, Yang Wang

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

In the present study, mechanism, origin of chemoselectivity, and substituent effects phosphine-catalyzed ring-opening reaction cyclopropyl ketone have been investigated using DFT method. Multiple pathways, including formation hydrofluorenone, Cloke-Wilson product, cyclopenta-fused were studied compared. The computational results show that pathway for hydrofluorenone is most favorable one, which involves four processes: nucleophilic substitution to open three-membered ring, an intramolecular Michael addition enolate intermediate, [1,5]-proton transfer give ylide, Wittig deliver final product. For disclosing structural analysis local reactivity index performed. Moreover, also considered QTAIM analysis. current study would provide useful insights understanding chemoselective reactions.

Language: Английский

Citations

1