Aromatic halogenation using carborane catalyst

Chem, Год журнала: 2023, Номер 10(1), С. 402 - 413

Опубликована: Ноя. 6, 2023

Язык: Английский

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Recent progress in the organoselenium-catalyzed difunctionalization of alkenes

Organic & Biomolecular Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Selenium-based catalysts have recently been utilized to facilitate a variety of new organic transformations, owing their intrinsic advantages, including low cost, toxicity, stability in both air and water, strong compatibility with diverse functional groups. The difunctionalization alkenes-the process incorporating two groups onto carbon-carbon double bond-has garnered particular interest within the chemical community its significant applications synthesis. Recently, organoselenium-catalyzed alkenes has emerged as an ideal powerful route obtain high-value vicinal difunctionalized molecules. This review emphasizes recent advancements this rapidly evolving field, focusing on scope, limitations, mechanisms various reactions.

Язык: Английский

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Telluronium‐Catalyzed Halogenation Reactions: Chalcogen‐Bond Activation of N‐Halosuccinimides and Catalysis

Chemistry - A European Journal, Год журнала: 2024, Номер 30(43)

Опубликована: Май 24, 2024

The ability of triaryltelluronium salts to interact with N-halosuccinimides (NXS) through chalcogen bonding (ChB) in the solid state and solution is demonstrated herein. Cocrystals bearing two CF

Язык: Английский

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Directing Group Strategy for the Isolation of Organoselenium(VI) Benzoselenonates: Metal-Free Catalysts for Hydrogen Evolution Reaction

Journal of the American Chemical Society, Год журнала: 2023, Номер 146(1), С. 57 - 61

Опубликована: Дек. 18, 2023

The exploration of fourth-period organoelements, particularly organoseleniums in their highest VI oxidation state, is limited owing to stability and synthesis. Herein, the isolation a new class quinolinyl-embedded, hexavalent selenium(VI) benzoselenonates has been discussed further evaluated for metal-free electrocatalytic hydrogen evolution reaction (HER). Se(VI) exhibited high Faradaic efficiency (F.E.) H2 gas production up 86% with very good turnover number (TON) 43 moderate overpotential (η) 500 mV; presence mild acetic acid source less deprotonating DMF solvent. Taken together various (NMR, UV–vis, EPR) spectroscopic DFT computation studies, plausible HER pathway proposed, which suggests that electrochemical reduction quinolinyl ring initiation step acts as site by involving hydridic type intermediate generation.

Язык: Английский

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Bromophosphatation as a Mode of Chiral Phosphoric Acid Catalyst Deactivation as Elucidated by Kinetic Profiling

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Май 20, 2025

A BINOL-derived chiral phosphoric acid (R)-1 was shown by kinetic profiling to be deactivated during the catalytic bromoesterification of cyclohexene. The products deactivation were identified as diastereoisomeric phosphates (R,1R,2R)-3a and (R,1S,2S)-3b are formed via an alkene bromophosphatation process where phosphate 1 behaves a competitive nucleophile, confirmed authentic preparations 3a 3b from stoichiometric reaction. HPLC separation diastereoisomers gave pure whose absolute relative configurations proven single-crystal X-ray diffraction. 31P{1H} NMR spectrum displayed four resonances despite having just one phosphorus atom, combined VT-NMR DFT analysis revealed this consequence rotational isomerism about 9-phenanthrene (Ar) bearing C3,3'-Ar bonds. Moreover, studies using variable time normalization (VTNA) cyclohexene showed first order kinetics in all reactants. amount under conditions quantified, enabling tracking temporal catalyst concentration hence elucidation 1. cycle consistent with these observations is proposed.

Язык: Английский

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Thianthrene/TfOH-catalyzed electrophilic halogenations using N-halosuccinimides as the halogen source

Chemical Science, Год журнала: 2024, Номер 15(32), С. 13058 - 13067

Опубликована: Янв. 1, 2024

A thianthrene (TT)/TfOH-catalyzed electrophilic halogenation has been developed, enabling broad substrate applicability and diverse types via the generation of a TT-based halogenated thianthrenium salt.

Язык: Английский

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Chalcogen Bond Catalysis with Telluronium Cations for Bromination Reaction: Importance of Electrostatic and Polarization Effects

Chemistry - A European Journal, Год журнала: 2023, Номер 29(71)

Опубликована: Сен. 25, 2023

Recently, chalcogen bond catalysts with telluronium cations have garnered considerable attention in organic reactions. In this work, catalysis on the bromination reaction of anisole N-bromosuccinimide (NBS) cationic has been explored density functional theory (DFT). The catalytic is divided into two stages: bromine transfer step and proton step. Based computational results, one can find rate-determining Moreover, present study elucidates that a stronger between NBS will give better performance. Additionally, work also clarified importance electrostatic polarization effects oxygen atom Te catalyst reaction. are significantly influenced by electron-withdrawing ability substitution groups catalysts. structure-property relationship strength bond, effect, effect performance established for design more efficient

Язык: Английский

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Both N-F oxidant and NaF determined reaction yield in the organoselenium-catalyzed oxidative ring-closing reaction of unsaturated alcohol: A theoretical study

Molecular Catalysis, Год журнала: 2024, Номер 567, С. 114442 - 114442

Опубликована: Авг. 13, 2024

Язык: Английский

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Benzoimidazolyl Organoseleniums: Antioxidant Activity and Catalysts for Selective Iodination of Arenes and Nitro-Michael Reaction

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(19), С. 14328 - 14340

Опубликована: Сен. 16, 2024

Here, the synthesis and catalytic activities of benzoimidazole-derived organoselenium compounds have been explored. The synthesized bis(2-benzoimidazolyl) diselenide, having increased Lewis acidity on selenium center, outperforms simple phenyl

Язык: Английский

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Halogen and Chalcogen Activation by Nucleophilic Catalysis

Chemistry - A European Journal, Год журнала: 2024, Номер unknown

Опубликована: Июль 23, 2024

Abstract The high utility of halogenated organic compounds has prompted the development numerous transformations that install carbon‐halogen motif. Halogen functionalities, deemed as “functional and functionalizable” molecules due to their capacity modulate diverse internal properties, constitute a pivotal strategy in drug discovery development. Traditional routes these building blocks have commonly involved multiple steps, harsh reaction conditions, use stoichiometric and/or toxic reagents. With emergence solid halogen carriers such N ‐halosuccinimides, halohydantoins popular sources halonium ions, past decade witnessed enormous growth new catalytic strategies for halofunctionalization. This review aims provide nuanced perspective on nucleophilic activators roles activation. It will highlight critical discoveries effecting racemic asymmetric variants reactions, driven by catalysts, activation modes, improved understanding chemical reactivity kinetics.

Язык: Английский

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