Elucidating the Mechanism and Selectivities of Cobalt‐Catalyzed Transformation of O‐Acyl Oxime DOI Open Access
Xiaohan Yu, Yang Wang

Applied Organometallic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 19, 2024

ABSTRACT In this work, the mechanistic investigation on cobalt‐catalyzed CH functionalization of O ‐acyl oxime and verification origin selectivities are employed using density functional theory (DFT) method. Based calculations, most energetically favorable pathway contains four steps: coordination Co(III) species to oxime, para ‐selective activation give a five‐membered cobaltacycle, [2,1]‐alkyne insertion, redox‐cyclization final product regenerate species. IRC calculations clearly indicate that process occurs in concerted but highly asynchronous manner. The structural analysis reveals ‐CH preferentially mainly due less steric hindrance. FMO energetic span model used disclose regioselectivity chemoselectivity, respectively.

Language: Английский

Carbene‐Catalyzed the Synthesis of 2‐Oxindole from Sulfonates and Isatin Derivatives DOI
Min Zhou, Min Ren,

Zhichuan Wang

et al.

ChemistrySelect, Journal Year: 2025, Volume and Issue: 10(21)

Published: June 1, 2025

Abstract A novel N‐heterocyclic carbene (NHC) catalyzed reaction between sulfonate and isatin derivatives has been successfully developed, enabling the efficient synthesis of a series 2‐oxindole derivatives. This catalytic system demonstrated remarkable efficiency, affording desired products in excellent yields up to 96%. Notably, exhibited significant stereoselectivity, with ratio cis ‐ trans configurations reaching Z:E = 1:10. Mechanistically, this methodology represents advancement NHC mediated activation sulfonyl compounds, providing new strategic approach for construction biologically important scaffolds. The developed protocol features mild conditions, broad substrate scope, high functional group tolerance, making it valuable addition synthetic toolbox.

Language: Английский

Citations

0
Mechanistic studies on phosphine-catalyzed [4 + 3] annulation of β′-acetoxy allenoate with 1C,3N-dinucleophile DOI

Kui Yuan,

Haoran Yang, Yang Wang

et al.

Computational and Theoretical Chemistry, Journal Year: 2024, Volume and Issue: 1241, P. 114924 - 114924

Published: Oct. 19, 2024

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
Uncovering a general oxidation model of nitrogen-containing oxidant in N-heterocyclic carbene (NHC) catalyzed oxidative reactions of aldehydes DOI
X.-J. Li, Xuan Wang, Yu Jia

et al.

Molecular Catalysis, Journal Year: 2024, Volume and Issue: 569, P. 114538 - 114538

Published: Sept. 13, 2024

Language: Английский

Citations

0
DFT Study in An Asymmetric Organocatalytic Homologation: Mechanism, Origin of Stereoselectivity DOI
Yang Wang, Donghui Wei

Asian Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 24, 2024

Abstract In the present study, mechanism, origin of stereoselectivity, and role catalyst organocatalytic homologation reaction between phenyl boronate trifluoromethyl diazomethane have been theoretically investigated using density functional theory (DFT) method. Based on calculations, in situ generated ethanol plays significant triggering reaction. Moreover, [1,2]‐boron migration process is stereoselectivity‐determining step, with S ‐configured isomer being predominantly. addition, NCI analysis performed to disclose stereoselectivity.

Language: Английский

Citations

0
Elucidating the Mechanism and Selectivities of Cobalt‐Catalyzed Transformation of O‐Acyl Oxime DOI Open Access
Xiaohan Yu, Yang Wang

Applied Organometallic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 19, 2024

ABSTRACT In this work, the mechanistic investigation on cobalt‐catalyzed CH functionalization of O ‐acyl oxime and verification origin selectivities are employed using density functional theory (DFT) method. Based calculations, most energetically favorable pathway contains four steps: coordination Co(III) species to oxime, para ‐selective activation give a five‐membered cobaltacycle, [2,1]‐alkyne insertion, redox‐cyclization final product regenerate species. IRC calculations clearly indicate that process occurs in concerted but highly asynchronous manner. The structural analysis reveals ‐CH preferentially mainly due less steric hindrance. FMO energetic span model used disclose regioselectivity chemoselectivity, respectively.

Language: Английский

Citations

0