Nickel-Catalyzed Enantioselective Reductive Aryl Fluoroalkenylation of Alkenes

ACS Catalysis, Год журнала: 2019, Номер 9(10), С. 9127 - 9133

Опубликована: Сен. 4, 2019

Enantioselective Ni-catalyzed reductive aryl monofluoroalkenylation of alkenes between bromides and gem-difluoroalkenes has been developed. The reaction proceeding under room temperature base-free conditions tolerates a wide range functional groups on both coupling partners. Various synthetically useful oxindoles containing monofluoroalkenyl substituent are obtained in good yields with 85%–95% enantiomeric excess. In addition, the synthetic method can be further applied to late-stage complex biologically active compounds.

Язык: Английский

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Dynamic Kinetic Cross-Electrophile Arylation of Benzyl Alcohols by Nickel Catalysis

Journal of the American Chemical Society, Год журнала: 2020, Номер 143(1), С. 513 - 523

Опубликована: Дек. 28, 2020

Catalytic transformation of alcohols via metal-catalyzed cross-coupling reactions is very important, but it typically relies on a multistep procedure. We here report dynamic kinetic approach for the direct functionalization alcohols. The feasibility this strategy demonstrated by nickel-catalyzed cross-electrophile arylation reaction benzyl with (hetero)aryl electrophiles. proceeds broad substrate scope both coupling partners. electron-rich, electron-poor, and ortho-/meta-/para-substituted electrophiles (e.g., Ar–OTf, Ar–I, Ar–Br, inert Ar–Cl) all coupled well. Most functionalities, including aldehyde, ketone, amide, ester, nitrile, sulfone, furan, thiophene, benzothiophene, pyridine, quinolone, Ar–SiMe3, Ar–Bpin, Ar–SnBu3, were tolerated. nature method enables benzylic alcohol in presence various nucleophilic groups, nonactivated primary/secondary/tertiary alcohols, phenols, free indoles. It thus offers robust alternative to existing methods precise construction diarylmethanes. synthetic utility was concise synthesis biologically active molecules its application peptide modification conjugation. Preliminary mechanistic studies revealed that situ formed oxalates nickel, possibly radical process, an initial step aryl

Язык: Английский

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Reductive dearomative arylcarboxylation of indoles with CO2 via visible-light photoredox catalysis

Nature Communications, Год журнала: 2020, Номер 11(1)

Опубликована: Июнь 29, 2020

Abstract Catalytic reductive coupling of two electrophiles and one unsaturated bond represents an economic efficient way to construct complex skeletons, which is dominated by transition-metal catalysis via electron transfer. Herein, we report a strategy visible-light photoredox-catalyzed successive single transfer, realizing dearomative arylcarboxylation indoles with CO 2 . This avoids common side reactions in catalysis, including ipso-carboxylation aryl halides β-hydride elimination. photoredox shows high chemoselectivity, low loading photocatalyst, mild reaction conditions (room temperature, 1 atm) good functional group tolerance, providing great potential for the synthesis valuable but difficultly accessible indoline-3-carboxylic acids. Mechanistic studies indicate that benzylic radicals anions might be generated as key intermediates, thus direction couplings other electrophiles, D O aldehyde.

Язык: Английский

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Broadly Applicable Directed Catalytic Reductive Difunctionalization of Alkenyl Carbonyl Compounds

Chem, Год журнала: 2020, Номер 6(3), С. 738 - 751

Опубликована: Янв. 16, 2020

Язык: Английский

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Enantioselective Radical Addition/Cross‐Coupling of Organozinc Reagents, Alkyl Iodides, and Alkenyl Boron Reagents

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(40), С. 14245 - 14249

Опубликована: Авг. 7, 2019

Abstract A hybrid transition‐metal/radical process is described that results in the addition of organozinc reagents and alkyl halides across alkenyl boron an enantioselective catalytic fashion. The reaction can be accomplished both intermolecularly intramolecularly, providing useful product yields high enantioselectivities manifolds.

Язык: Английский

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