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

Tiantian Feng,

Da‐Gang Zhou

и другие.

Journal of Chemical Information and Modeling, Год журнала: 2025, Номер unknown

Опубликована: Фев. 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.

Язык: 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

и другие.

The Journal of Physical Chemistry A, Год журнала: 2024, Номер 128(30), С. 6190 - 6198

Опубликована: Июль 18, 2024

N-heterocyclic carbene (NHC)-bound

Язык: Английский

Процитировано

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

Meng-Qing Yang,

Yang Wang

Molecular Catalysis, Год журнала: 2024, Номер 567, С. 114445 - 114445

Опубликована: Авг. 10, 2024

Язык: Английский

Процитировано

4
Mechanisms of C(sp3)-H Functionalization of Acetonitrile or Acetone with Alkynes: A DFT Investigation DOI
Bin Chen,

Tiantian Feng,

Da‐Gang Zhou

и другие.

Journal of Chemical Information and Modeling, Год журнала: 2025, Номер unknown

Опубликована: Фев. 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.

Язык: Английский

Процитировано

0