Chiral Oxazaborolidinium Ion (COBI)-Catalyzed Reaction of Aldimine with Tributyltin Cyanide: Mechanism and Origin of Stereoselectivity DOI
Yan-Li Shi,

Yaqian Shi,

Shanxiao Yang

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(14), P. 9803 - 9810

Published: July 3, 2023

By conducting density functional theory (DFT) calculations, the detailed reaction mechanisms of aldimines with tributyltin cyanide under catalytic influence chiral oxazaborolidinium ion (COBI) have been uncovered. Three potential pathways were examined, and two stereoselective routes determined for most energetically favorable mechanism. In primary route, a proton is transferred from COBI catalyst to aldimine substrate, which then followed by C–C bond formation produce final product. Subsequently, NBO analyses stereoselectivity-determining transition states conducted identify crucial role hydrogen interactions in controlling stereoselectivity. These computed findings should prove invaluable comprehending underlying origins stereoselectivity COBI-mediated reactions this type.

Language: Английский

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
Synthesis of Cobalt Complexes and Study of Their Catalytic Activities in Various Organic Transformations DOI

Krishna Sri Dosapati,

Dripta De Joarder

Springer proceedings in physics, Journal Year: 2024, Volume and Issue: unknown, P. 87 - 108

Published: Dec. 28, 2024

Language: Английский

Citations

0
Chiral Oxazaborolidinium Ion (COBI)-Catalyzed Reaction of Aldimine with Tributyltin Cyanide: Mechanism and Origin of Stereoselectivity DOI
Yan-Li Shi,

Yaqian Shi,

Shanxiao Yang

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(14), P. 9803 - 9810

Published: July 3, 2023

By conducting density functional theory (DFT) calculations, the detailed reaction mechanisms of aldimines with tributyltin cyanide under catalytic influence chiral oxazaborolidinium ion (COBI) have been uncovered. Three potential pathways were examined, and two stereoselective routes determined for most energetically favorable mechanism. In primary route, a proton is transferred from COBI catalyst to aldimine substrate, which then followed by C–C bond formation produce final product. Subsequently, NBO analyses stereoselectivity-determining transition states conducted identify crucial role hydrogen interactions in controlling stereoselectivity. These computed findings should prove invaluable comprehending underlying origins stereoselectivity COBI-mediated reactions this type.

Language: Английский

Citations

1