Electrocatalysis as an enabling technology for organic synthesis

Chemical Society Reviews, Год журнала: 2021, Номер 50(14), С. 7941 - 8002

Опубликована: Янв. 1, 2021

Electrochemistry has recently gained increased attention as a versatile strategy for achieving challenging transformations at the forefront of synthetic organic chemistry. Electrochemistry's unique ability to generate highly reactive radical and ion intermediates in controlled fashion under mild conditions inspired development number new electrochemical methodologies preparation valuable chemical motifs. Particularly, recent developments electrosynthesis have featured an use redox-active electrocatalysts further enhance control over selective formation downstream reactivity these intermediates. Furthermore, electrocatalytic mediators enable proceed manner that is mechanistically distinct from purely methods, allowing subversion kinetic thermodynamic obstacles encountered conventional synthesis. This review highlights key innovations within past decade area electrocatalysis, with emphasis on mechanisms catalyst design principles underpinning advancements. A host oxidative reductive are discussed grouped according classification transformation nature electrocatalyst.

Язык: Английский

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Recent advances in visible light-activated radical coupling reactions triggered by (i) ruthenium, (ii) iridium and (iii) organic photoredox agents

Chemical Society Reviews, Год журнала: 2021, Номер 50(17), С. 9540 - 9685

Опубликована: Янв. 1, 2021

Visible light-activated reactions continue to expand and diversify. The example shown here is a Birch reduction achieved by organophotoredox reagents.

Язык: Английский

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Electrophotocatalysis: Combining Light and Electricity to Catalyze Reactions

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(28), С. 12567 - 12583

Опубликована: Июль 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.

Язык: Английский

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

Angewandte Chemie International Edition, Год журнала: 2021, Номер 61(12)

Опубликована: Сен. 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.

Язык: Английский

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

Nature Catalysis, Год журнала: 2022, Номер 5(10), С. 943 - 951

Опубликована: Окт. 10, 2022

Язык: Английский

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Electrochemical Late-Stage Functionalization

Chemical Reviews, Год журнала: 2023, Номер 123(19), С. 11269 - 11335

Опубликована: Сен. 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.

Язык: Английский

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Electrophotocatalytic C−H Heterofunctionalization of Arenes

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(20), С. 11163 - 11167

Опубликована: Март 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.

Язык: Английский

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Photoelectrochemical Asymmetric Catalysis Enables Direct and Enantioselective Decarboxylative Cyanation

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(44), С. 20201 - 20206

Опубликована: Окт. 31, 2022

The development of efficient and sustainable methods for decarboxylative transformations is great importance due to the ease availability nontoxicity carboxylic acids. Despite tremendous efforts in this area, it remains challenging develop enantioselective direct from Herein we disclose a photoelectrocatalytic method cyanation. photoelectrochemical reactions convert acids enantioenriched nitriles by employing cerium/copper relay catalysis with cerium salt catalytic decarboxylation chiral copper complex stereoselective C-CN formation.

Язык: Английский

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Red Light-Based Dual Photoredox Strategy Resembling the Z-Scheme of Natural Photosynthesis

JACS Au, Год журнала: 2022, Номер 2(6), С. 1488 - 1503

Опубликована: Июнь 10, 2022

Photoredox catalysis typically relies on the use of single chromophores, whereas strategies, in which two different light absorbers are combined, rare. In photosystems I and II green plants, separate chromophores P680 P700 both absorb independently one another, then their excitation energy is combined so-called Z-scheme, to drive an overall reaction that thermodynamically very demanding. Here, we adapt this concept perform photoredox reactions organic substrates with input red photons instead blue or UV light. Specifically, a CuI bis(α-diimine) complex combination situ formed 9,10-dicyanoanthracenyl radical anion presence excess diisopropylethylamine catalyzes ca. 50 dehalogenation detosylation reactions. This dual approach seems useful because less damaging has greater penetration depth than radiation. UV-vis transient absorption spectroscopy reveals subtle change solvent from acetonitrile acetone induces changeover mechanism, involving either dominant photoinduced electron transfer triplet-triplet pathway. Our study illustrates mechanistic complexity systems operating under multiphotonic conditions, it provides insights into how competition between desirable unwanted steps can become more controllable.

Язык: Английский

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Photoelectrochemical Asymmetric Catalysis Enables Enantioselective Heteroarylcyanation of Alkenes via C–H Functionalization

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(34), С. 18753 - 18759

Опубликована: Авг. 15, 2023

The asymmetric difunctionalization of alkenes, a method transforming readily accessible alkenes into enantioenriched chiral structures high value, has long been focal point organic synthesis. Despite tremendous efforts in this domain, it remains considerable challenge to devise enantioselective oxidative dicarbofunctionalization even though these transformations can utilize stable and unfunctionalized functional group donors. In context, we report herein photoelectrocatalytic for the heteroarylcyanation aryl which employs heteroarenes through C-H functionalization. photoelectrochemical catalysis (PEAC) combines photoredox electrocatalysis facilitate formation two C-C bonds operating via hydrogen (H2) evolution obviating need external chemical oxidants.

Язык: Английский

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