(Z)-Selective Isomerization of 1,1-Disubstituted Alkenes by Scandium-Catalyzed Allylic C–H Activation

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(39), С. 26766 - 26776

Опубликована: Сен. 20, 2024

The isomerization of 1,1-disubstituted alkenes through 1,3-hydrogen shift is an atom-efficient route for synthesizing trisubstituted alkenes, which are important moieties in many natural products, pharmaceuticals, and organic materials. However, this reaction often encounters regio- stereoselectivity challenges, typically yielding

Язык: Английский

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Catalytic asymmetric olefin isomerization: Facile access to chiral carbon-stereogenic olefinic compounds

Chem Catalysis, Год журнала: 2022, Номер 2(11), С. 2852 - 2864

Опубликована: Сен. 16, 2022

Язык: Английский

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Iron‐Catalyzed Positional and Geometrical Isomerization of Alkenes

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(8), С. 1100 - 1111

Опубликована: Фев. 20, 2023

Abstract This review outlines the most noteworthy achievements of last few years in renascent field positional and geometrical isomerization alkenes using iron catalysis, from a mechanistic perspective. Particular attention will be placed on developments beyond seminal contributions carbonyl complexes their aspects underlying nature active species. The relevant literature has been covered until late 2022. magnified image

Язык: Английский

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Asymmetric dihydroboration of allenes enabled by ligand relay catalysis

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Сен. 18, 2024

Язык: Английский

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N₂ Dissociation vs Reversible 1,2-Methyl Migration in PC_NHCP Cobalt(I) Complexes in the Stereoselective Isomerization (E/Z) of Allyl Ethers

JACS Au, Год журнала: 2024, Номер 4(11), С. 4234 - 4248

Опубликована: Сен. 18, 2024

With growing efforts pushing toward sustainable catalysis, using earth-abundant metals has become increasingly important. Here, we present the first examples of cobalt PC

Язык: Английский

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Asymmetric Olefin Isomerization via Phase-Transfer-Catalyzed [1,3]-Hydrogen Transfer for Access to Axially Chiral Furan-Benzimidazoles

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Май 9, 2025

An efficient catalytic asymmetric olefin isomerization of axially chiral methylene dihydrofuran-benzimidazoles via kinetic resolution is reported. Under mild phase-transfer catalysis, furan-benzimidazole compounds and recovered were obtained in high ee. The combination the TBD-catalyzed provided access to both enantiomers furan-benzimidazoles. Deuterium-labeling experiments reveal intramolecular [1,3]-H transfer mechanism. utility this method was demonstrated by scale-up synthesis functionalization products.

Язык: Английский

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DFT investigation of photocatalytic contra-thermodynamic alkene isomerization in α-substituted alkenylazaarenes

Molecular Catalysis, Год журнала: 2025, Номер 583, С. 115215 - 115215

Опубликована: Май 22, 2025

Язык: Английский

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Palladium‐Catalyzed Long‐Range Isomerization of Aryl Olefins

Chinese Journal of Chemistry, Год журнала: 2022, Номер 40(19), С. 2269 - 2275

Опубликована: Июнь 14, 2022

Comprehensive Summary Long‐range olefin isomerization could lead to the remote functionalization of hydrocarbon chains, which is advantageous with regards atom‐, step‐, and redox economy. However, present methodologies for long‐range are mainly focused on heteroatom directed migration; studies using aryl groups as directing group limited. The limited examples either utilize olefins special substituted a benzene ring, or use elaborately optimized ligands co‐catalysts accelerate isomerization. A more simple catalytic system general olefins, without need co‐catalysts, was be developed. Herein, we report Pd‐catalyzed (up 15 units) via 1,2‐hydrogen shift mechanism. This methodology provides pathway participation co‐catalysts.

Язык: Английский

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Cobalt-Catalyzed Migration Isomerization of Dienes

Organic Letters, Год журнала: 2022, Номер 24(25), С. 4592 - 4597

Опубликована: Июнь 21, 2022

A cobalt-catalyzed multipositional isomerization of conjugated dienes has been reported for the first time using an 8-oxazoline iminoquinoline ligand. This reaction is operationally simple and atom-economical readily available starting materials with E/Z mixture to access disubstituted 1,3-dienes excellent yields good E,E stereoselectivity. The mechanism via alkene insertion cobalt hydride species β-H elimination a π-allyl intermediate proposed on basis deuterium labeling control experiments density functional theory calculations.

Язык: Английский

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Cobalt-Hydride-Catalyzed Alkene-Carboxylate Transposition (ACT) of Allyl Carboxylates

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(46), С. 31391 - 31399

Опубликована: Ноя. 12, 2024

The alkene-carboxylate transposition (ACT) of allyl carboxylates is one the most atom-economic and synthetically reliable transformations in organic chemistry, as are versatile synthetic intermediates. Classic ACT transformations, including [3,3]-sigmatropic rearrangement transition metal-catalyzed allylic rearrangement, typically yield 1,2-alkene/1,3-acyloxy shifted products through a two-electron process. However, position-altered to produce distinct 1,3-alkene/1,2-acyloxy remains elusive. Here, we report first cobalt-hydride-catalyzed carboxylates, enabling access these unprecedented via 1,2-radical migration (RaM) strategy. This transformation demonstrates broad functional group tolerance, suitable for late-stage modification complex molecules, amenable gram-scale synthesis. It also expands reaction profiles both cobalt catalysis. Preliminary experimental computational studies suggest mechanism involving metal-hydride hydrogen atom transfer (MHAT) 1,2-RaM expected serve basis development Co-H-catalyzed generating wide array valuable building blocks synthetic, medicinal, materials chemistry.

Язык: Английский

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