Photoredox-Catalyzed C–H Functionalization Reactions

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 1925 - 2016

Published: Sept. 29, 2021

The fields of C–H functionalization and photoredox catalysis have garnered enormous interest utility in the past several decades. Many different scientific disciplines relied on strategies including natural product synthesis, drug discovery, radiolabeling, bioconjugation, materials, fine chemical synthesis. In this Review, we highlight use reactions. We separate review into inorganic/organometallic catalysts organic-based catalytic systems. Further subdivision by reaction class─either sp2 or sp3 functionalization─lends perspective tactical for these methods synthetic applications.

Language: Английский

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Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2017 - 2291

Published: Nov. 23, 2021

We present here a review of the photochemical and electrochemical applications multi-site proton-coupled electron transfer (MS-PCET) in organic synthesis. MS-PCETs are redox mechanisms which both an proton exchanged together, often concerted elementary step. As such, MS-PCET can function as non-classical mechanism for homolytic bond activation, providing opportunities to generate synthetically useful free radical intermediates directly from wide variety common functional groups. introduction practitioner’s guide reaction design, with emphasis on unique energetic selectivity features that characteristic this class. then chapters oxidative N–H, O–H, S–H, C–H homolysis methods, generation corresponding neutral species. Then, reductive PCET activations involving carbonyl, imine, other X═Y π-systems, heteroarenes, where ketyl, α-amino, heteroarene-derived radicals be generated. Finally, we asymmetric catalysis materials device applications. Within each chapter, subdivide by group undergoing homolysis, thereafter type transformation being promoted. Methods published prior end December 2020 presented.

Language: Английский

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Organic thermally activated delayed fluorescence (TADF) compounds used in photocatalysis

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(13), P. 7587 - 7680

Published: Jan. 1, 2021

Organic compounds that show Thermally Activated Delayed Fluorescence (TADF) have become wildly popular as next generation emitters in organic light-emitting diodes (OLEDs), but since 2016, received significant and increasing attention photocatalysts.

Language: Английский

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Photoinduced intermolecular hydrogen atom transfer reactions in organic synthesis

Chem Catalysis, Journal Year: 2021, Volume and Issue: 1(3), P. 523 - 598

Published: May 24, 2021

Language: Английский

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Photocatalytic Late-Stage C–H Functionalization

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(8), P. 4237 - 4352

Published: Jan. 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.

Language: Английский

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Radical Carboxylative Cyclizations and Carboxylations with CO₂

Accounts of Chemical Research, Journal Year: 2021, Volume and Issue: 54(10), P. 2518 - 2531

Published: May 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.

Language: Английский

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Reductive radical-polar crossover: traditional electrophiles in modern radical reactions

Chemical Science, Journal Year: 2019, Volume and Issue: 10(36), P. 8285 - 8291

Published: Jan. 1, 2019

The concept of reductive radical-polar crossover (RRPCO) reactions has recently emerged as a valuable and powerful tool to overcome limitations both radical traditional polar chemistry.

Language: Английский

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Visible-Light-Driven Reductive Carboarylation of Styrenes with CO₂ and Aryl Halides

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(18), P. 8122 - 8129

Published: April 20, 2020

The first example of visible-light-driven reductive carboarylation styrenes with CO2 and aryl halides in a regioselective manner has been achieved. A broad range iodides bromides were compatible this reaction. Moreover, pyridyl halides, alkyl even chlorides also viable method. These findings may stimulate the exploration novel Meerwein arylation-addition reactions user-friendly as radical sources photocatalytic utilization CO2.

Language: Английский

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Formation of Hierarchical FeCoS₂–CoS₂ Double‐Shelled Nanotubes with Enhanced Performance for Photocatalytic Reduction of CO₂

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(29), P. 11918 - 11922

Published: April 29, 2020

Hierarchical FeCoS2 -CoS2 double-shelled nanotubes have been rationally designed and constructed for efficient photocatalytic CO2 reduction under visible light. The synthetic strategy, engaging the two-step cation-exchange reactions, precisely integrates two metal sulfides into a tubular heterostructure with both of shells assembled from ultrathin two-dimensional (2D) nanosheets. Benefiting distinctive structure composition, hybrid can reduce bulk-to-surface diffusion length photoexcited charge carriers to facilitate their separation. Furthermore, this expose abundant active sites enhancing adsorption surface-dependent redox harvest incident solar irradiation more efficiently by light scattering in complex interior. As result, these hierarchical exhibit superior activity high stability photosensitized deoxygenative reduction, affording CO-generating rate 28.1 μmol h-1 (per 0.5 mg catalyst).

Language: Английский

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Cooperative NHC and Photoredox Catalysis for the Synthesis of β‐Trifluoromethylated Alkyl Aryl Ketones

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(45), P. 19956 - 19960

Published: July 23, 2020

Despite the great potential of radical chemistry in organic synthesis, N-heterocyclic carbene (NHC)-catalyzed reactions involving intermediates are not well explored. This communication reports three-component coupling aroyl fluorides, styrenes and Langlois reagent (CF3 SO2 Na) to give various β-trifluoromethylated alkyl aryl ketones with good functional group tolerance moderate high yields by cooperative photoredox/NHC catalysis. The alkene acyltrifluoromethylation proceeds via radical/radical cross ketyl radicals benzylic C-radicals. generated SET reduction situ formed acylazolium ions whereas derive from trifluoromethyl addition onto styrenes.

Language: Английский

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