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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Recent advances in radical-mediated transformations of 1,3-dienes

CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION), Journal Year: 2022, Volume and Issue: 43(3), P. 548 - 557

Published: Feb. 2, 2022

Language: Английский

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

Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 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 (

Language: Английский

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Electro‐mediated PhotoRedox Catalysis for Selective C(sp³)–O Cleavages of Phosphinated Alcohols to Carbanions

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(38), P. 20817 - 20825

Published: June 24, 2021

We report a novel example of electro-mediated photoredox catalysis (e-PRC) in the reductive cleavage C(sp

Language: Английский

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Merging Carbonyl Addition with Photocatalysis

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(8), P. 1135 - 1147

Published: March 31, 2022

The carbonyl group stands as a fundamental scaffold and plays ubiquitous role in synthetically important chemical reactions both academic industrial contexts. Venerable transformations, including the aldol reaction, Grignard Wittig Nozaki-Hiyama-Kishi constitute vast empowering synthetic arsenal. Notwithstanding, two-electron mechanisms inherently confine breadth of accessible reactivity topological patterns.Fostered by rapid development photoredox catalysis, combing well-entrenched addition radicals can harness several unique increasingly sustainable transformations. In particular, unusual carbon-carbon carbon-heteroatom disconnections, which are out reach chemistry, be conceived. To meet this end, novel strategy toward utilization simple compounds intermolecular radical acceptors was developed. reaction is enabled visible-light photoredox-initiated hole catalysis. situ Brønsted acid activation moiety prevents β-scission from occurring. Furthermore, regioselective alkyl obviates use metals, ligands, or additives, thus offering high degree atom economy under mild conditions. On basis same concept work Schindler co-workers, carbonyl-olefin cross-metathesis, induced visible light, has also been achieved, leveraging Prins-elimination sequence.Recently, dual chromium catalysis developed us Kanai, complementary approach to revered reaction. Leveraging intertwined synergy between light metal, radical-to-polar crossover transformations eminent molecular motifs have Reactions such redox-neutral allylation aldehydes alkylation harvest power enable catalytic metal. Overall, exquisite levels diastereoselectivity enforced via highly compact transition states. Other examples, dialkylation 1,3-dienes propargylation portray versatile combination multicomponent coupling endeavors. Highly valuable motifs, commonly occur complex drug natural product architectures, now accessed single operational step. Going beyond addition, seminal contributions Fagnoni MacMillan preconized photocatalytic HAT-based acyl formation key aldehyde valorization strategy. Our articulated concept, carboxy hydrogen abstractors regio- chemoselective alkynylation trifluoromethylthiolation.This Account, narrative our others' at interface radical-based photochemistry, aims provide core guiding foundations disruptive developments. We envisage that extending crossovers manifolds, taming less-activated carbonyls, processes, merging electron steps with energy-transfer events will propel breakthroughs near future.

Language: Английский

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Photocatalytic Umpolung Strategy for the Synthesis of α-Amino Phosphine Oxides and Deuterated Derivatives

Organic Letters, Journal Year: 2023, Volume and Issue: 25(44), P. 8016 - 8021

Published: Oct. 30, 2023

Direct, economical, and green synthesis of deuterated α-amino phosphine oxides remains an elusive challenge in synthetic chemistry. Herein, we report a visible-light-driven umpolung strategy for synthesizing from isocyanide using 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene as the photocatalyst D2O deuterium source. Moreover, streamlined sustainable methodology can be applied modification amino acids, natural products, drugs. The strong antiproliferative activity desired products indicates that method could provide novel privileged scaffold antitumor drug development.

Language: Английский

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Advances in photoinduced radical–polar crossover cyclization (RPCC) of bifunctional alkenes

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 11(3), P. 895 - 915

Published: Dec. 20, 2023

Photoinduced radical–polar crossover cyclization (RPCC) of bifunctional alkenes is high synthetic utility to produce cyclic products with precise alkene design. This review summarizes the recent representative advances in field RPC.

Language: Английский

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Polyoxometalate‐dependent Photocatalytic Activity of Radical‐doped Perylenediimide‐based Hybrid Materials

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(17)

Published: Jan. 2, 2024

Abstract Inorganic‐organic hybrid materials are a kind of multiduty with high crystallinity and definite structures, built from functional inorganic organic components highly tunable photochemical properties. Perylenediimides (PDIs) strong visible light‐absorbing dyes π‐electron‐deficient planes properties depending on their micro‐environment, which provides platform for designing efficient photocatalytic materials. Herein, four radical‐doped PDI‐based crystalline materials, Cl 4 ‐PDI⋅SiW 12 O 40 ( 1 ), ‐PDI⋅SiMo 2 ‐PDI⋅PW 3 ‐PDI⋅PMo were attained by slow diffusion polyoxometalates (POMs) into acidified ‐PDI solutions. The obtained not only exhibited prominent photochromism, but also possessed reactive radicals under ambient conditions. Furthermore, all could be easily photoreduced to radical anions (Cl ‐PDI⋅ − then underwent second photoexcitation form energetic excited state −* ). However, experiments theoretical calculations demonstrated that the formed showed unusual POM‐dependent efficiencies toward oxidative coupling amines iodoperfluoroalkylation alkenes; higher found (anion: SiW 4− ) SiMo compared PW 3− PMo these mainly controlled energy differences between SOMO‐2 level LUMO POMs. structure‐photocatalytic activity relationships established in present work provide new research directions both photocatalysis material fields, will promote integration areas explore interesting

Language: Английский

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Cyclic Amine Synthesis via Catalytic Radical‐Polar Crossover Cycloadditions

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(18)

Published: Feb. 29, 2024

Abstract The rapid assembly of valuable cyclic amine architectures in a single step from simple precursors has been recognized as an ideal platform term efficiency and sustainability. Although vast number studies regarding synthesis reported, new synthetic disconnection approaches are still high demand. Herein, we report catalytic radical‐polar crossover cycloaddition to triggered primary sulfonamide under photoredox condition. This newly developed disconnection, comparable established approaches, will allow construct β, β‐disubstituted β‐monosubstituted derivatives efficiently. study highlights the unique utility bifunctional reagent, which acts radical precursor nucleophile. open‐shell methodology demonstrates broad tolerance various functional groups, drug natural products economically sustainable fashion.

Language: Английский

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