Visible-Light-Induced Energy-Transfer-Mediated Hydrofunctionalization and Difunctionalization of Unsaturated Compounds via Sigma-Bond Homolysis of Energy-Transfer Acceptors

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1854 - 1941

Published: Jan. 17, 2025

Over the past decade, visible-light-mediated energy-transfer (EnT) catalysis, particularly triplet–triplet (TTEnT) has emerged as a mild and environmentally friendly approach for diverse organic synthetic transformations. In contrast to photoredox which typically requires sacrificial electron donors or acceptors complete catalytic cycle, EnT photocatalysis generally proceeds with high atom economy while minimizing generation of wasteful byproducts. Furthermore, successful catalysis is contingent upon precise control redox potentials both photocatalysts substrates, strategies are primarily influenced by triplet energy compatibility between these entities. Considering growing importance photocatalysis, well hydrofunctionalization difunctionalization reactions in synthesis, this review systematically summarizes significant advancements EnT-enabled unsaturated compounds via sigma-bond homolysis over decade. Special emphasis placed on elucidating substrate scopes mechanistic scenarios. Additionally, discusses versatile applications methodologies addresses current challenges opportunities within evolving research field. This structured into six main categories based different types sigma-bonds undergoing homolysis. These include transformations mediated 1) N–O bond oxime esters other N,O-radical precursors; 2) N–S N-sulfonyl imines N,S-radical 3) chalcogen–chalcogen disulfides oxy/thio/selenosulfonates; 4) C–S tri/difluoromethylated sulfinates, acetylenic triflones, arylsulfonium salts; 5) C–X (X = halogen) halides; 6) acceptors. Through providing theoretical backgrounds along comprehensive overview currently employed acceptors, photosensitizers, contemporary EnT-induced compounds, aims serve an invaluable resource future innovations rapidly

Language: Английский

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Visible-Light-Catalyzed Tandem Radical Addition/1,5-Hydrogen Atom Transfer/Cyclization of 2-Alkynylarylethers with Sulfonyl Chlorides

Organic Letters, Journal Year: 2022, Volume and Issue: 24(25), P. 4704 - 4709

Published: June 20, 2022

A novel visible-light-catalyzed tandem radical addition/1,5-hydrogen atom transfer/cyclization cascade of 2-alkynylarylethers with sulfonyl chlorides in 2-methyltetrahydrofuran was developed under photocatalyst- and additive-free conditions. This reaction relies on unique energy transfer solvent-radical relay strategies to generate radicals for the preparation a series sulfonyl-functionalized dihydrobenzofurans moderate high yields catalyzed by visible light or solar radiation.

Language: Английский

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Radical Polychloromethylation/Cyclization of Unactivated Alkenes: Access to Polychloromethyl‐Substituted Ring‐Fused Quinazolinones

Advanced Synthesis & Catalysis, Journal Year: 2022, Volume and Issue: 364(6), P. 1085 - 1090

Published: Feb. 10, 2022

Abstract A radical di‐ and trichloromethylation/cyclization of unactivated alkenes was developed with commercially available dichloromethane chloroform as di‐and trichloromethyl sources under metal‐free conditions. Variously substituted trichloromethylated pyrrolo‐ piperidino‐quinazolinones were obtained in 47–94% yields. Additionally, dibromomethylation/cyclization also achieved standard conditions when CH 2 Br utilized. Moreover, the dichloromethylated product can be transformed into 1′ H ‐spiro[cyclopropane‐1,3′‐pyrrolo[2,1‐ b ]quinazolin]‐9′(2′ )‐one after treating by KOH. magnified image

Language: Английский

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Electrophotocatalytic tri- or difluoromethylative cyclization of alkenes

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(10), P. 2482 - 2490

Published: Jan. 1, 2023

Photoelectrocatalysis is mild yet potent and this work unlocks the potential of unactivated alkenes for oxidant-free oxidative cyclization alkenes.

Language: Английский

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Radical-mediated photoredox hydroarylation with thiosulfonate

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(19), P. 2767 - 2770

Published: Jan. 1, 2023

Radical-mediated photoredox hydroarylation reaction of unactivated alkenes using thiosulfonate compounds as key radical precursors to synthesize pyridyquinazolinone and pyrroloquinazolinone derivatives is described.

Language: Английский

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Metal-Free Photoinduced Hydrocyclization of Unactivated Alkenes toward Ring-Fused Quinazolin-4(3H)-ones via Intermolecular Hydrogen Atom Transfer

Organic Letters, Journal Year: 2023, Volume and Issue: 25(10), P. 1683 - 1688

Published: March 8, 2023

A visible-light-induced hydrocyclization of unactivated alkenes was developed using 3CzClIPN as the photocatalyst to generate substituted α-methyldeoxyvasicinones and α-methylmackinazolinones in moderate good yields. An intermolecular hydrogen atom transfer with THF source involved. Mechanism studies indicated that intramolecular addition situ formed aminal radical alkene generated polycyclic quinazolinone.

Language: Английский

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Radical Cascade Cyclization of Alkene‐Tethered Compounds: Versatile Approach towards Ring‐Fused Polycyclic Structures

Asian Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 12(5)

Published: April 8, 2023

Abstract Ring‐fused polycyclic structures widely exist in a myriad of natural products and pharmaceutical molecules. Consequently, the construction such from readily available substrates becomes an important researching topic organic synthesis. Triggered by addition radicals to (activated or unactivated) double bonds alkenes, subsequent intramolecular addition/cyclization leads compounds. Following this procedure, variety functionalized ring‐fused were formed. Great achievements have been witnessed recently. Those works provided efficient, atom economy, operational simple approaches toward versatile alkene‐based substrates. Here, we summarized recent on formation via radical‐triggered cascade reactions alkenes. Construction with no less than 3 fused rings developed during last decade included Review, corresponding mechanisms also discussed.

Language: Английский

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Photoredox streamlines electrocatalysis: photoelectrosynthesis of polycyclic pyrimidin-4-ones through carbocyclization of unactivated alkenes with malonates

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(7), P. 4199 - 4208

Published: Jan. 1, 2024

A new photoelectrocatalytic mode permits the synthesis of polycyclic pyrimidin-4-ones through dehydrogenative cyclization malonates with unactivated alkenes.

Language: Английский

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Photocatalytic Sulfonylation: Innovations and Applications

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: July 14, 2024

Photosynthesis, converting sustainable solar energy into chemical energy, has emerged as a promising craft to achieve diverse organic transformations due its mild reaction conditions, sustainability, and high efficiency. The synthesis of sulfonated compounds drawn significant attention in the pharmaceuticals, agrochemicals, materials industries unique structure electronic properties sulfonyl groups. Over past decades, many photocatalytic sulfonylation reactions have been developed. In this review, recent advances photocatalyzed reviewed since 2020, with primary focus on discussing design mechanism.

Language: Английский

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Organic photoredox catalytic radical sulfonamidation/cyclization of unactivated alkenes towards polycyclic quinazolinones

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(22), P. 6290 - 6294

Published: Jan. 1, 2022

The synthesis of sulfonamidylated polycyclic quinazolinones was developed via visible-light-induced radical sulfonamidation/cyclization unactivated alkenes using 4CzIPN as the photocatalyst.

Language: Английский

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