Photoredox/Nickel Dual Catalysis-Enabled Aryl Formylation with 2,2-Dimethoxy-N,N-dimethylethan-1-amine as CO Source

Organic Letters, Год журнала: 2024, Номер 26(7), С. 1478 - 1482

Опубликована: Фев. 9, 2024

Herein, a dual photoredox/nickel catalyzed formylation of aryl bromide with commercially available 2,2-dimethoxy-N,N-dimethylethan-1-amine as an effective CO source has been successfully achieved, delivering series aromatic aldehydes in moderate to good yields. Compared the traditional reductive carbonylation process, this newly designed synthetic protocol provides straightforward toolbox access aldehydes, obviating use carbon monoxide and stoichiometric reductants. Finally, utility direct reaction was demonstrated pharmaceutical analogue synthesis.

Язык: Английский

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Sulfonamide-directed site-selective functionalization of unactivated C(sp3)−H enabled by photocatalytic sequential electron/proton transfer

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

Опубликована: Июнь 14, 2024

Abstract The generation of alkyl radical from C(sp 3 )−H substrates via hydrogen atom abstraction represents a desirable yet underexplored strategy in alkylation reaction since involving common concerns remain adequately unaddressed, such as the harsh conditions, limited substrate scope, and employment noble metal- or photo-catalysts stoichiometric oxidants. Here, we utilize synergistic photoredox transfer (HAT) catalysis to accomplish general practical functionalization unactived centers with broad high functional group compatibility, operational simplicity. A combination validation experiments density theory reveals that N-centered radicals, generated free N − H bond stepwise electron/proton event, are key intermediates enable an intramolecular 1,5-HAT intermolecular HAT process for nucleophilic carbon-centered radicals formation achieve heteroarylation, alkylation, amination, cyanation, azidation, trifluoromethylthiolation, halogenation deuteration. value this protocol is further demonstrated by gram-scale synthesis late-stage natural products drug derivatives.

Язык: Английский

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Amine-Borane-Mediated, Nickel/Photoredox-Catalyzed Cross-Electrophile Coupling between Alkyl and Aryl Bromides

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(17), С. 12658 - 12667

Опубликована: Авг. 19, 2024

Nickel/photoredox catalysis has emerged as a powerful platform for exploring nontraditional and challenging cross-couplings. Herein, metallaphotoredox catalytic protocol been developed on the basis of tertiary amine-ligated boryl radical-induced halogen atom transfer process under blue-light irradiation. A wide variety aryl heteroaryl bromides featuring different functional groups pharmaceutical moieties were facilely coupled to rapidly install C(sp3)-enriched aromatic scaffolds. The compatibility Lewis base-ligated borane with nickel was well exemplified extend chemical space Ni-catalyzed cross-electrophile coupling.

Язык: Английский

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Visible Light-Induced, Nickel-Catalyzed Late-Stage 4-Alkylation of Hantzsch Esters with Alkyl Bromide

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(15), С. 10987 - 10997

Опубликована: Июль 22, 2024

Herein, visible light-induced, nickel-catalyzed direct functionalization of the Hantzsch esters (HEs) with readily accessible alkyl bromides has been successfully achieved by taking advantage HE as reductant and substrate through an aromatization-dearomatization process. In this strategy, single electron reduction reactive Ni(I) species is essential for success late-stage transformation. A wide range 4-alkyl-1,4-dihydropyridines were rapidly assembled in moderate to good yields under mild conditions, rendering photoinduced approach attractive synthetic medicinal chemistry.

Язык: Английский

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One-pot Multicomponent Tandem Reaction for the Rapid Synthesis of 2-Amino-3-benzylindoles

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

Опубликована: Янв. 1, 2025

A novel one-pot oxidative cross-dehydrogenation coupling (CDC) reaction has been developed for the selective construction of C–N and C–C bonds at C2,3-positions indoles.

Язык: Английский

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MeOH-Triggered Halogen-Atom Transfer of Unactivated Alkyl Bromides Enabling the Photoredox Giese Addition

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 18, 2025

Herein, a nickel-catalyzed, photoredox Giese addition reaction with readily accessible alkyl bromides, driven by available feedstock MeOH as the halogen-atom transfer (XAT) reagent, was successfully achieved under mild conditions. The versatility of this protocol demonstrated through range structurally varied bromides and Giese-type acceptors moderate to good yields. Mechanistic investigation highlights that formation radicals XAT tentatively prompted •CH2OH, which derived from sequential photo-oxidation/1,2-hydrogen-atom MeOH.

Язык: Английский

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Nickel/Photoredox Dual-Catalyzed, Regioselective 1,2-Carboacylation of Alkenes via Synergistic Alkyl and Benzoyl Radical Coupling

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Май 2, 2025

A regioselective 1,2-carboacylation protocol of alkenes via nickel/photoredox dual catalysis has been successfully developed under mild conditions. wide range alkyl bromides, α-oxocarboxylic acids, and styrenes proved to be compatible the optimized conditions, affording corresponding products in up 91% yields. Mechanistically, key success this approach is temporal orchestration radical generation: nickel-catalyzed halogen atom transfer (XAT) for bromides photoredox-driven decarboxylation acids.

Язык: Английский

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Site-Selective Functionalization of Unactivated C(sp3)–H Bonds via Synergistic Merger of Photoredox and HAT Catalysis

Research Square (Research Square), Год журнала: 2024, Номер unknown

Опубликована: Фев. 1, 2024

Hydrogen atom abstraction from C(sp³)−H substrates for the generation of alkyl radical represents a desirable yet underexplored strategy in alkylation reaction since involving noble metal catalysts, stoichiometric oxidants, and limited scope are common drawbacks. Here we describe synergistic utilization photoredox hydrogen transfer (HAT) catalysis to accomplish general practical functionalization unactived centers, which features broad scope, high functional group compatibility, operational simplicity. A combination validation experiments density theory reveals that N-centred radicals, generated free N−H bond via catalyzed single-electron oxidation followed by deprotonation stepwise electron/proton event, key intermediates enable an intramolecular 1,5-HAT or intermolecular HAT process nucleophilic carbon-centred radicals formation achieve heteroarylation, alkylation, amination, cyanation, azidation, trifluoromethylthiolation, halogenation deuteration. The value this protocol was further demonstrated gram-scale synthesis late-stage natural products drug derivatives.

Язык: Английский

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Chemical Space Localization for Unknown Metabolite Annotation via Semantic Similarity of Mass Spectral Language

bioRxiv (Cold Spring Harbor Laboratory), Год журнала: 2024, Номер unknown

Опубликована: Июнь 3, 2024

ABSTRACT Untargeted metabolomics, employing liquid chromatography‒mass spectrometry (LC-MS), allows quantification of known and unidentified metabolites within biological systems. However, in practical metabolomic studies, the majority often remain unidentified. Here, we developed a novel deep learning-based metabolite annotation approach via semantic similarity analysis mass spectral language. This enables prediction structurally related for unknown compounds. By considering chemical space, these provide valuable information about potential location assist ranking candidates obtained from molecular structure databases. Validated with benchmark datasets, our method has consistently demonstrated superior performance compared to existing methods annotation. In case study involving Qianxi cultivar cherry tomato, reaffirmed well-established biomarkers ripening processes identified set promising rational new biomarker metabolites. Overall, presented exhibits significant annotating metabolites, particularly revealing “dark matter” untargeted metabolomics.

Язык: Английский

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Recent advances in photocatalytic C-H amination to nitrogenous structures

Green Synthesis and Catalysis, Год журнала: 2024, Номер unknown

Опубликована: Окт. 1, 2024

Язык: Английский

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