Copper catalysed construction of C-P bond: C-H functionalization

Journal of Organometallic Chemistry, Год журнала: 2025, Номер unknown, С. 123512 - 123512

Опубликована: Янв. 1, 2025

Язык: Английский

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Electrochemical generation of aryl radicals from organoboron reagents enabled by pulsed electrosynthesis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(31)

Опубликована: Май 16, 2024

Aryl radicals play a pivotal role as reactive intermediates in chemical synthesis, commonly arising from aryl halides and diazo compounds. Expanding the repertoire of sources for radical generation to include abundant stable organoboron reagents would significantly advance chemistry broaden their reactivity profile. While traditional approaches utilize stoichiometric oxidants or photocatalysis generate these reagents, electrochemical conditions have been largely underexplored. Through rigorous mechanistic investigations, we identified fundamental challenges hindering generation. In addition high oxidation potentials aromatic compounds, electrode passivation through grafting, homocoupling radicals, decomposition issues were identified. We demonstrate that pulsed electrosynthesis enables selective efficient by mitigating challenges. Our discoveries facilitated development first conversion potassium trifluoroborate salts into C-P bonds. This sustainable straightforward oxidative approach exhibited broad substrate scope, accommodating various heterocycles chlorides, typical substrates transition-metal catalyzed cross-coupling reactions. Furthermore, extended this methodology form C-Se, C-Te, C-S bonds, showcasing its versatility potential bond formation processes.

Язык: Английский

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Access to Benzyl Oxindoles via Electron Donor‐Acceptor Complex Photoactivation Using Thianthrenium Salts and Potassium Carbonate

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(11), С. 2587 - 2595

Опубликована: Апрель 19, 2024

Abstract A photochemical synthesis of biologically relevant benzyl oxindoles is presented via electron‐donor acceptor (EDA) complex strategy. This exogenous photocatalyst‐free method describes the formation a new electron donor‐acceptor based on potassium carbonate and thianthrenium salts for C( sp 2 )−C( 3 ) bond formation. transition‐metal free reaction allows rapid increase in molecular complexity chemical space, tolerating different functional groups as well sophisticated biomolecules. The scalability sustainability this highlighted by an important waste recovery protocol. Mechanistic investigations support EDA that induces radical chain, applicability showcased straightforward derivatization reactions.

Язык: Английский

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Transition Metal and Photocatalyst Free Arylation via Photoexcitable Electron Donor Acceptor Complexes:Mediation and Catalysis

ChemCatChem, Год журнала: 2024, Номер 16(11)

Опубликована: Янв. 15, 2024

Abstract Visible‐light‐activated organic reactions unlock novel avenues for complex molecular transformations, impossible under standard “thermal” conditions, which makes them powerful tools in the arsenal of synthetic chemistry. However, transition metal‐based or photoredox catalysts are often used to ensure productive absorption visible light, might be not desirable medicinal chemistry and industry due toxicity, low sustainability, high cost most photocatalysts. A more environmentally economically benign approach is based on formation transient electron donor‐acceptor (EDA) complexes between two reagents a reagent an additive, that readily absorb acting as internal photosensitizers. Within EDA complex‐based arylation strategies, chemical transformations mediated by noncovalent interaction molecules, namely electron‐poor aryl halides their equivalents electron‐rich nucleophilic additives. Moreover, besides stoichiometric organocatalysis can achieved certain cases through regeneration donor molecules course reaction. Photoexcitation induces single transfer (SET) process generate radical species step. This Review will focus state‐of‐the‐art strategies utilizing halides, aryldiazonium, diaryliodonium, arylsulfonium arylphosphonium salts reactants, published mainly last five years.

Язык: Английский

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Site‐Selective S‐Arylation of 1‐Thiosugars with Aryl Thianthrenium Salts through Copper(I)‐Mediated, Photoredox‐ Catalyzed Reactions

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(10), С. 2344 - 2351

Опубликована: Апрель 5, 2024

Abstract A process for the synthesis of aryl thioglycosides from thianthrenium salts and 1‐thiosugars is achieved by copper(I)‐mediated, photoredox‐catalyzed reactions. The desired products could be obtained in 32% to 78% yield after irradiation with 34 W blue light at room temperature. Various functional groups, especially including halogen were well tolerated under standard reaction conditions. This strategy differs conceptually all previous S ‐glycosylations that thiosugar functionality incorporated into complex natural or drugs a late stage site‐selectively, which has not been shown via halides aryldiazonium salts.

Язык: Английский

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Energy-transfer-enabled photocatalytic transformations of aryl thianthrenium salts

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

Опубликована: Ноя. 8, 2024

Aryl thianthrenium salts are valuable in photocatalysis but traditionally require external electron donors for activation. This study introduces an energy transfer (EnT) strategy the activation of aryl using 2,3,4,5,6-penta(carbazol-9-yl)benzonitrile (5CzBN) as a metal-free photocatalyst, eliminating need donors. Utilizing this EnT approach, we achieve C-H deuteration arenes under visible light with CDCl

Язык: Английский

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Recent Progress in C–S Bond Formation via Electron Donor-Acceptor Photoactivation

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

Опубликована: Янв. 1, 2025

This review summarizes recent progress in EDA complex-promoted C–S bond formation using various sulfur-containing substrates under mild conditions via visible light irradiation.

Язык: Английский

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Development of Trp-AuNPs-rGO based electrochemical active biosensing interface for dopamine detection

Chemical Physics Impact, Год журнала: 2024, Номер unknown, С. 100726 - 100726

Опубликована: Сен. 1, 2024

Язык: Английский

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Organocatalytic access to 3-pyridylphosphonates from vinyl phosphonates and aldehydes

Chemical Communications, Год журнала: 2024, Номер 60(40), С. 5306 - 5309

Опубликована: Янв. 1, 2024

The preparation of 3-phosphorylated pyridines has remained the most challenging compared to corresponding 2- or 4-functionalized pyridines.

Язык: Английский

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Thianthrenium salts to arynes: base promoted C‐N bond construction

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер unknown

Опубликована: Окт. 18, 2024

Abstract Amines are widely found in natural products, drugs and pesticides. We have proposed a base‐promoted method for synthesizing polysubstituted aromatic amines. The reaction does not necessitate the involvement of transition metals, provided that an equivalent base is employed. In this process, aryl thianthrenium salt serves as precursor to arynes, which subsequently distorted by induction effect different substituents. attack amine nucleophiles results formation series multi‐substituted products.

Язык: Английский

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