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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Organocatalytic Asymmetric Electrophilic Amination of Allylic Boronates

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 17935 - 17944

Published: Nov. 20, 2024

The asymmetric addition of allylic boronates to electrophiles is a powerful method for preparing chiral molecules bearing synthetically valuable moieties. While effective catalytic methods exist, they have so far been limited the enantioselective allyl- and crotyl-boration carbonyl compounds imines, thereby forming C–C bonds. Here, we present strategy that expands scope this platform include stereoselective formation C–N We identified an inexpensive readily available diol catalyzes azodicarboxylates, affording hydrazides with high stereocontrol. This electrophilic amination chemistry shows broad substrate requires mild conditions, proceeding at ambient temperature. Mechanistic studies reveal catalyst facilitates boronate through reversible exchange boron's achiral alkoxy ligand. By coordination azodicarboxylate, substrates mutually activate each other, allowing transfer allyl group.

Language: Английский

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Allylboration of Ketones Catalyzed by BINOL Derivatives: Which Species Are Involved Depending on Substrate Reactivity?

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(18), P. 13224 - 13234

Published: Sept. 11, 2024

Allylboration reactions of ketones catalyzed by BINOL derivatives can exhibit highly variable stereochemical courses depending on the nature and reactivity ketone substrate. In this Article, we put into perspective relationship between starting material active species involved in asymmetric allyboration derivatives. This work, aimed at comparing different plausible mechanisms density functional theory (DFT) M06-2X/6-311+G(d,p) level involving types allylboronates presence organocatalyst, leads to confirmation hitherto accepted hypothesis a reaction promoted transient cyclic allyl-1,3,2-dioxaborolane derived from BINOLs case unactivated or weakly activated such as indanone. A hypothetical scenario dimeric boronate chiral catalysts was also investigated.

Language: Английский

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Photochemical Carboborylation and Three-component Difunctionalization of α,β-unsaturated Ketones with Boronic Acids via Tosylhydrazones

Chemical Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

The photochemical carboborylation of α,β-unsaturated tosylhydrazones with boronic acids gives tertiary allylboronates. A one pot sequence involving an aldehyde allylation provides a powerful three-component method for diversity oriented synthesis.

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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