Visible Light-Induced Transition Metal Catalysis

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 1543 - 1625

Опубликована: Окт. 8, 2021

In recent years, visible light-induced transition metal catalysis has emerged as a new paradigm in organic photocatalysis, which led to the discovery of unprecedented transformations well improvement known reactions. this subfield complex serves double duty by harvesting photon energy and then enabling bond forming/breaking events mostly via single catalytic cycle, thus contrasting established dual photocatalysis an exogenous photosensitizer is employed. addition, approach often synergistically combines catalyst–substrate interaction with photoinduced process, feature that uncommon conventional photoredox chemistry. This Review describes early development advances emerging field.

Язык: Английский

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Aminoalkyl radicals as halogen-atom transfer agents for activation of alkyl and aryl halides

Science, Год журнала: 2020, Номер 367(6481), С. 1021 - 1026

Опубликована: Фев. 27, 2020

Organic halides are important building blocks in synthesis, but their use (photo)redox chemistry is limited by low reduction potentials. Halogen-atom transfer remains the most reliable approach to exploit these substrates radical processes despite its requirement for hazardous reagents and initiators such as tributyltin hydride. In this study, we demonstrate that α-aminoalkyl radicals, easily accessible from simple amines, promote homolytic activation of carbon-halogen bonds with a reactivity profile mirroring classical tin radicals. This strategy conveniently engages alkyl aryl wide range redox transformations construct sp3-sp3, sp3-sp2, sp2-sp2 carbon-carbon under mild conditions high chemoselectivity.

Язык: Английский

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Generation of Alkyl Radicals: From the Tyranny of Tin to the Photon Democracy

Chemical Reviews, Год журнала: 2020, Номер 120(17), С. 9790 - 9833

Опубликована: Авг. 6, 2020

Alkyl radicals are key intermediates in organic synthesis. Their classic generation from alkyl halides has a severe drawback due to the employment of toxic tin hydrides point that "flight tyranny tin" radical processes was considered for long time an unavoidable issue. This review summarizes main alternative approaches unstabilized radicals, using photons as traceless promoters. The recent development photochemical and photocatalyzed enabled discovery plethora new precursors, opening world chemistry broader community, thus allowing era photon democracy.

Язык: Английский

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Visible light photocatalysis in the late-stage functionalization of pharmaceutically relevant compounds

Chemical Society Reviews, Год журнала: 2020, Номер 50(2), С. 766 - 897

Опубликована: Дек. 22, 2020

Recent developments and future prospects of visible-light photocatalysis in the late-stage functionalization pharmaceuticals natural bioactive compounds.

Язык: Английский

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Photocatalytic Late-Stage C–H Functionalization

Chemical Reviews, Год журнала: 2023, Номер 123(8), С. 4237 - 4352

Опубликована: Янв. 24, 2023

The emergence of modern photocatalysis, characterized by mildness and selectivity, has significantly spurred innovative late-stage C–H functionalization approaches that make use low energy photons as a controllable source. Compared to traditional strategies, photocatalysis paves the way toward complementary and/or previously unattainable regio- chemoselectivities. Merging compelling benefits with workflow offers potentially unmatched arsenal tackle drug development campaigns beyond. This Review highlights photocatalytic strategies small-molecule drugs, agrochemicals, natural products, classified according targeted bond newly formed one. Emphasis is devoted identifying, describing, comparing main mechanistic scenarios. draws critical comparison between established ionic chemistry photocatalyzed radical-based manifolds. aims establish current state-of-the-art illustrate key unsolved challenges be addressed in future. authors aim introduce general readership functionalization, specialist practitioners evaluation methodologies, potential for improvement, future uncharted directions.

Язык: Английский

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Transition Metal-Catalyzed Organic Reactions under Visible Light: Recent Developments and Future Perspectives

ACS Catalysis, Год журнала: 2020, Номер 10(16), С. 9170 - 9196

Опубликована: Июль 20, 2020

The development of transition metal (TM) catalysis for organic synthesis under visible light without recourse to typical photoredox catalysts has become a rapidly growing area research and been actively explored in the past several years. Distinct from extensively developed catalysis, which photocatalyst generally does not directly participate bond-forming process, photocatalyst/TM synergistic absorbs photon energy transfers TM catalyst through redox or transfer this Review focuses on summarizing recent developments photocatalytic reactions that use complexes both absorb catalytic bond formation involving covalently bonded intermediate. contents are categorized by used (Pd, Cu, Co, Ni, Mn, Au, Rh, Fe, Ru), with descending sequence according number examples reported each metal, provide an overview April 2020. Future perspectives personal opinions regarding expanding field also discussed.

Язык: Английский

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Radical Carboxylative Cyclizations and Carboxylations with CO₂

Accounts of Chemical Research, Год журнала: 2021, Номер 54(10), С. 2518 - 2531

Опубликована: Май 6, 2021

ConspectusCarbon dioxide (CO2) is not only a greenhouse gas and common waste product but also an inexpensive, readily available, renewable carbon resource. It important one-carbon (C1) building block in organic synthesis for the construction of valuable compounds. However, its utilization challenging owing to thermodynamic stability kinetic inertness. Although significant progress has been achieved, many limitations remain this field with regard substrate scope, reaction system, activation strategies.Since 2015, our group focused on CO2 synthesis. We are interested vast possibilities radical chemistry, although high reactivity radicals presents challenges controlling selectivity. hope develop highly useful transformations involving by achieving balance selectivity under mild conditions. Over past 6 years, we along other experts have disclosed radical-type carboxylative cyclizations carboxylations using CO2.We initiated research realizing Cu-catalyzed oxytrifluoromethylation allylamines heteroaryl methylamines generate 2-oxazolidones various precursors. Apart from Cu catalysis, visible-light photoredox catalysis powerful method achieve efficient cyclization. In these cases, single-electron-oxidation-promoted C–O bond formation between benzylic carbamates key step.Since carboxylic acids exist widely natural products bioactive drugs serve as bulk chemicals industry, realized further visible-light-promoted construct such chemicals. achieved selective umpolung imines, enamides, tetraalkylammonium salts, oxime esters successive single-electron-transfer (SSET) reduction. Using strategy, dearomative arylcarboxylation indoles CO2. addition incorporation 1 equiv per substrate, recently developed photoredox-catalyzed dicarboxylation alkenes, allenes, (hetero)arenes via SSET reduction, which allows two molecules into compounds diacids polymer precursors.In two-electron CO2, sought new strategies realize single-electron Inspired hypothetical electron-transfer mechanism iron–sulfur proteins, visible-light-driven thiocarboxylation alkenes catalytic iron salts promoters. The in-situ-generated Fe/S complexes likely able reduce anion, could react give stabilized radical. Moreover, charge-transfer complex (CTC) thiolate acrylate/styrene hydrocarboxylation generation or alkene anion. On basis novel CTC, organocatalytic Hantzsch ester effective reductant.

Язык: Английский

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Irradiation-Induced Heck Reaction of Unactivated Alkyl Halides at Room Temperature

Journal of the American Chemical Society, Год журнала: 2017, Номер 139(50), С. 18307 - 18312

Опубликована: Ноя. 8, 2017

The palladium-catalyzed Mizoroki–Heck reaction is arguably one of the most significant carbon–carbon bond-construction reactions to be discovered in last 50 years, with a tremendous number applications production chemicals. This Nobel-Prize-winning transformation has yet overcome obstacle its general application range alkyl electrophiles, especially tertiary halides that possess eliminable β-hydrogen atoms. Whereas cross-coupling utilize ground-state reactivity palladium complexes under thermal conditions and generally apply single ligand system, we report Heck proceeds smoothly at room temperature variety tertiary, secondary, primary bromides upon irradiation blue light-emitting diodes presence dual phosphine system. We rationalize this unprecedented achieved by utilizing photoexcited-state complex enhance oxidative addition suppress undesired β-hydride elimination.

Язык: Английский

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C–H functionalization reactions enabled by hydrogen atom transfer to carbon-centered radicals

Chemical Science, Год журнала: 2020, Номер 11(48), С. 12974 - 12993

Опубликована: Янв. 1, 2020

Intramolecular and intermolecular HAT to C-centered radicals enables selective C–H functionalization of organic molecules.

Язык: Английский

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Catalysis with Palladium Complexes Photoexcited by Visible Light

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(34), С. 11586 - 11598

Опубликована: Янв. 2, 2019

Abstract Palladium catalysis induced by visible light is an emerging field of catalysis. In contrast to classical reactions catalyzed Pd complexes in the ground state, which mostly proceed through two‐electron redox processes, mechanisms these new methods based on photoexcited usually operate transfer a single electron. Such processes lead putative hybrid Pd/radical species, exhibit both radical and Pd‐type reactivity. This Minireview highlights recent progress this rapidly growing area.

Язык: Английский

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