Scalable Photoelectrochemical Dehydrogenative Cross‐Coupling of Heteroarenes with Aliphatic C−H Bonds

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(34), P. 14275 - 14280

Published: June 3, 2020

Heteroarenes are structural motifs found in many bioactive compounds and functional materials. Dehydrogenative cross-coupling of heteroarenes with aliphatic C-H bonds provides straightforward access to functionalized from readily available Established methods employ stoichiometric chemical oxidants under conditions heating or light irradiation. By merging electrochemistry photochemistry, we have achieved efficient photoelectrochemical dehydrogenative C(sp3 )-H donors through H2 evolution, without the addition metal catalysts oxidants. Mechanistically, donor is converted a nucleophilic carbon radical H-atom transfer chlorine atom, which produced by irradiation anodically generated Cl2 Cl- . The then undergoes substitution heteroarene afford alkylated products.

Language: Английский

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Electrophotocatalytic Decarboxylative C−H Functionalization of Heteroarenes

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(26), P. 10626 - 10632

Published: March 30, 2020

Abstract Decarboxylative C−H functionalization reactions are highly attractive methods for forging carbon–carbon bonds considering their inherent step‐ and atom‐economical features the pervasiveness of carboxylic acids bonds. An ideal approach to achieve these dehydrogenative transformations is through hydrogen evolution without using any chemical oxidants. However, effective couplings by decarboxylative bond formation with proton reduction remain an unsolved challenge. Herein, we report electrophotocatalytic that merges organic electrochemistry photocatalysis efficient direct alkylation carbamoylation heteroaromatic compounds evolution. This method, which combines high efficiency selectivity in promoting decarboxylation superiority effecting reduction, enables coupling a wide range bases variety oxamic acids. Advantageously, this method scalable decagram amounts, applicable late‐stage drug molecules.

Language: Английский

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Electrophotocatalysis: Combining Light and Electricity to Catalyze Reactions

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(28), P. 12567 - 12583

Published: July 11, 2022

Visible-light photocatalysis and electrocatalysis are two powerful strategies for the promotion of chemical reactions that have received tremendous attention in recent years. In contrast, processes combine these modalities, an area termed electrophotocatalysis, until recently remained quite rare. However, over past several years a number reports this shown potential combining power light electrical energy to realize new catalytic transformations. Electrophotocatalysis offers ability perform photoredox without need large quantities stoichiometric or superstoichiometric oxidants reductants by making use electrochemical as electron source sink. addition, electrophotocatalysis is readily amenable generation open-shell photocatalysts, which tend exceptionally strong redox potentials. way, potent yet selective been realized under relatively mild conditions. This Perspective highlights advances provides some possible avenues future work growing area.

Language: Английский

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Electrophotocatalytic Undirected C−H Trifluoromethylations of (Het)Arenes

Chemistry - A European Journal, Journal Year: 2019, Volume and Issue: 26(15), P. 3241 - 3246

Published: Dec. 25, 2019

Electrophotochemistry has enabled arene C-H trifluoromethylation with the Langlois reagent CF3 SO2 Na under mild reaction conditions. The merger of electrosynthesis and photoredox catalysis provided a chemical oxidant-free approach for generation radical. electrophotochemistry was carried out in an operationally simple manner, setting stage challenging trifluoromethylations unactivated arenes heteroarenes. robust nature electrophotochemical manifold reflected by wide scope, including electron-rich electron-deficient benzenes, as well naturally occurring Electrophotochemical further achieved flow modular electro-flow-cell equipped in-operando monitoring unit on-line flow-NMR spectroscopy, providing support single electron transfer processes.

Language: Английский

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Electrochemical generation of nitrogen-centered radicals for organic synthesis

Green Synthesis and Catalysis, Journal Year: 2021, Volume and Issue: 2(2), P. 165 - 178

Published: March 29, 2021

There is a resurgence of interests in organic electrochemistry, which generally accepted as green synthetic tool. In this context, many electrochemical methods have been developed the past decade to access various nitrogen-centered radicals (NCRs) from readily available precursors controlled fashion, enabling rapid development NCR-mediated new reactions for construction nitrogen-containing compounds. review, recent advances chemistry electrochemically generated NCRs are critically highlighted, based on strategies their formation and types NCRs. Focus put mechanism generation different applications.

Language: Английский

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Synthetic Molecular Photoelectrochemistry: New Frontiers in Synthetic Applications, Mechanistic Insights and Scalability

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 61(12)

Published: Sept. 3, 2021

Synthetic photoelectrochemistry (PEC) is receiving increasing attention as a new frontier for the generation and handling of reactive intermediates. PEC permits selective single-electron transfer (SET) reactions in much greener way broadens redox window possible transformations. Herein, most recent contributions are reviewed, demonstrating exciting opportunities, namely, combination with other reactivity paradigms (hydrogen-atom transfer, radical polar crossover, energy sensitization), scalability up to multigram scale, novel selectivities SET super-oxidations/reductions importance precomplexation temporally enable excited ion catalysis.

Language: Английский

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Photoelectrochemical asymmetric catalysis enables site- and enantioselective cyanation of benzylic C–H bonds

Nature Catalysis, Journal Year: 2022, Volume and Issue: 5(10), P. 943 - 951

Published: Oct. 10, 2022

Language: Английский

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Electrochemical Late-Stage Functionalization

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(19), P. 11269 - 11335

Published: Sept. 26, 2023

Late-stage functionalization (LSF) constitutes a powerful strategy for the assembly or diversification of novel molecular entities with improved physicochemical biological activities. LSF can thus greatly accelerate development medicinally relevant compounds, crop protecting agents, and functional materials. Electrochemical synthesis has emerged as an environmentally friendly platform transformation organic compounds. Over past decade, electrochemical late-stage (eLSF) gained major momentum, which is summarized herein up to February 2023.

Language: Английский

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Hole-mediated photoredox catalysis: tris(p-substituted)biarylaminium radical cations as tunable, precomplexing and potent photooxidants

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(6), P. 1132 - 1142

Published: Jan. 1, 2021

Triarylamines are demonstrated as novel, tunable electroactivated photocatalysts that use dispersion precomplexation to harness the full potential of visible photon (>4.0 V vs. SCE) in anti-Kasha photo(electro)chemical super-oxidations arenes.

Language: Английский

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Electrophotocatalytic C−H Heterofunctionalization of Arenes

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(20), P. 11163 - 11167

Published: March 4, 2021

The electrophotocatalytic heterofunctionalization of arenes is described. Using 2,3-dichloro-5,6-dicyanoquinone (DDQ) under a mild electrochemical potential with visible-light irradiation, undergo oxidant-free hydroxylation, alkoxylation, and amination high chemoselectivity. In addition to batch reactions, an recirculating flow process demonstrated, enabling the conversion benzene phenol on gram scale.

Language: Английский

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