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

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 2017 - 2291

Опубликована: Ноя. 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.

Язык: Английский

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

Chemical Society Reviews, Год журнала: 2021, Номер 50(13), С. 7587 - 7680

Опубликована: Янв. 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.

Язык: Английский

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Non-innocent Radical Ion Intermediates in Photoredox Catalysis: Parallel Reduction Modes Enable Coupling of Diverse Aryl Chlorides

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(29), С. 10882 - 10889

Опубликована: Июль 13, 2021

We describe a photocatalytic system that elicits potent photoreductant activity from conventional photocatalysts by leveraging radical anion intermediates generated in situ. The combination of an isophthalonitrile photocatalyst and sodium formate promotes diverse aryl coupling reactions abundant but difficult to reduce chloride substrates. Mechanistic studies reveal two parallel pathways for substrate reduction both enabled key terminal reductant byproduct, carbon dioxide anion.

Язык: Английский

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Acridinium Salts and Cyanoarenes as Powerful Photocatalysts: Opportunities in Organic Synthesis

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(36), С. 19526 - 19549

Опубликована: Апрель 22, 2021

The use of organic photocatalysts has revolutionized the field photoredox catalysis, as it allows access to reactivities that were traditionally restricted transition-metal photocatalysts. This Minireview reports recent developments in acridinium ions and cyanoarene derivatives synthesis. activation inert chemical bonds well late-stage functionalization biorelevant molecules are discussed, with a special focus on their mechanistic aspects.

Язык: Английский

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Recent advances of visible-light photocatalysis in the functionalization of organic compounds

Journal of Photochemistry and Photobiology C Photochemistry Reviews, Год журнала: 2022, Номер 50, С. 100488 - 100488

Опубликована: Фев. 2, 2022

Язык: Английский

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The advent and development of organophotoredox catalysis

Chemical Communications, Год журнала: 2021, Номер 58(9), С. 1263 - 1283

Опубликована: Дек. 10, 2021

We herein discuss how and when organic photocatalysts can efficiently replace or outperform their metal counterparts.

Язык: Английский

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Visible light photocatalysis in the synthesis of pharmaceutically relevant heterocyclic scaffolds

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(5), С. 1485 - 1507

Опубликована: Янв. 1, 2022

Visible light and photoredox catalysis have emerged as a powerful long-lasting tool for organic synthesis, demonstrating the importance of variety chemical bond formation methods.

Язык: Английский

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Formation and degradation of strongly reducing cyanoarene-based radical anions towards efficient radical anion-mediated photoredox catalysis

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Янв. 6, 2023

Cyanoarene-based photocatalysts (PCs) have attracted significant interest owing to their superior catalytic performance for radical anion mediated photoredox catalysis. However, the factors affecting formation and degradation of cyanoarene-based PC (PC•‒) are still insufficiently understood. Herein, we therefore investigate PC•‒ under widely-used photoredox-mediated reaction conditions. By screening various PCs, elucidate strategies efficiently generate with adequate excited-state reduction potentials (Ered*) via supra-efficient generation long-lived triplet excited states (T1). To thoroughly behavior in actual reactions, a reductive dehalogenation is carried out as model identified dominant photodegradation pathways PC•‒. Dehalogenation coexistent depending on rate electron transfer (ET) substrate strongly depends electronic steric properties PCs. Based understanding both PC•‒, demonstrate that efficient highly reducing allows catalyzed aryl/alkyl halides at loading low 0.001 mol% high oxygen tolerance. The present work provides new insights into reactions reactions.

Язык: Английский

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Recent advances of decatungstate photocatalyst in HAT process

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(13), С. 2523 - 2538

Опубликована: Янв. 1, 2024

The decatungstate anion (W

Язык: Английский

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The Golden Age of Thermally Activated Delayed Fluorescence Materials: Design and Exploitation

Chemical Reviews, Год журнала: 2024, Номер unknown

Опубликована: Дек. 12, 2024

Since the seminal report by Adachi and co-workers in 2012, there has been a veritable explosion of interest design thermally activated delayed fluorescence (TADF) compounds, particularly as emitters for organic light-emitting diodes (OLEDs). With rapid advancements innovation materials design, efficiencies TADF OLEDs each primary color points well white devices now rival those state-of-the-art phosphorescent emitters. Beyond electroluminescent devices, compounds have also found increasing utility applications numerous related fields, from photocatalysis, to sensing, imaging beyond. Following our previous review 2017 (

Язык: Английский

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