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

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

Published: Aug. 10, 2024

Language: Английский

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Theoretical Investigation on A Chiral Brønsted acid (CBA)-Catalyzed Isomerization Reaction of BCB: Mechanism and Origin of Stereoselectivity

New Journal of Chemistry, Journal Year: 2024, Volume and Issue: 48(25), P. 11360 - 11365

Published: Jan. 1, 2024

The mechanism, role of catalyst and origin stereoselectivity for the isomerization reaction BCB catalyzed by a chiral Brønsted acid (CBA) have been revealed in detail using DFT calculations.

Language: Английский

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

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

Published: Jan. 6, 2025

Language: Английский

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Theoretical Studies on the Competing Mechanism and Origin of Diastereoselectivity of NHC-Catalyzed Intramolecular [3 + 2] Annulations of Ynals

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

Published: March 5, 2025

Chiral tricyclic 6,5,5-fused rings exhibit structural diversity and possess important biological activities in the synthesis of natural products. However, predicting possible mechanism origin stereoselectivity these reactions remains a challenge. In this article, we conducted theoretical investigation into NHC-catalyzed intramolecular [3 + 2] annulations ynals to generate rings. Our calculations revealed that NHC could nucleophilically attack carbonyl group ynal reactant, leading formation Breslow intermediate via 1,2-proton transfer. Subsequently, an Michael addition takes place, resulting 6-5 bicyclic intermediate. We then compared competitive processes involving proton transfer Mannich reaction. The more energetically favorable process involves HOAc-assisted process, followed by To ascertain diastereoselectivity, performed noncovalent interaction (NCI) atom-in-molecule (AIM) analyses. This work is useful for understanding general principles detailed mechanisms chiral scaffolds with unique diastereoselectivity.

Language: Английский

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

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

Published: Oct. 19, 2024

Language: Английский

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DFT Study on the Mechanism of Phosphine-Catalyzed Ring-Opening Reaction of Cyclopropyl Ketone

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

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Mechanisms and Origins of Regio- and Stereoselectivities in NHC-Catalyzed [3 + 3] Annulation of α-Bromoenals and 5-Aminoisoxazoles: A DFT Study

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(15), P. 10748 - 10759

Published: July 12, 2024

Density functional theory (DFT) calculations were conducted to explore the mechanisms and origins of regio- stereoselectivities underlying [3 + 3] annulation reaction between α-bromoenals 5-aminoisoxazoles with

Language: Английский

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DFT Study in An Asymmetric Organocatalytic Homologation: Mechanism, Origin of Stereoselectivity

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

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Elucidating the Mechanism and Selectivities of Cobalt‐Catalyzed Transformation of O‐Acyl Oxime

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

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