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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Three-Component Photochemical 1,2,5-Trifunctionalizations of Alkenes toward Densely Functionalized Lynchpins

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(43), P. 23814 - 23823

Published: Oct. 18, 2023

Radical remote 1,n-difunctionalization reactions (n > 2) of alkenes are powerful tools to efficiently introduce functional groups with selected distances into target molecules. Among these reactions, 1,5-difunctionalizations an important subclass, leading sought-after scaffolds, but typically suffer from tailored starting materials and strict limitations for the formed group in 2-position. Seeking address issues make radical more applicable, we report a novel three-component 1,2,5-trifunctionalization reaction between imine-based bifunctional reagents two distinct alkenes, driven by visible light energy transfer-catalysis. Key achieving this selective one-step installation three different via choreographed formation four bonds was utilization 1,2-boron shift rigorous capitalization polarities stabilities. Thorough mechanistic studies were carried out, synthetic utility obtained products demonstrated various downstream modifications. Notably, addition functionalization individual groups, their interplay gave rise unique array cyclic products.

Language: Английский

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Access to chiral β-amino sulfones from acrylamides and sulfur dioxide by iron catalysis

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(6), P. 1678 - 1684

Published: Jan. 1, 2024

This method allows for the enantioselective synthesis of β-azide sulfones via iron-catalyzed vicinal azide-sulfonylation acrylamides. It makes first instance achieving asymmetric construction through iron catalysis with SO 2 insertion.

Language: Английский

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Recent Advances in Nickel-Catalyzed Ring Opening Cross-Coupling of Aziridines

Acta Chimica Sinica, Journal Year: 2024, Volume and Issue: 82(2), P. 190 - 190

Published: Jan. 1, 2024

Language: Английский

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Deep eutectic solvents as sustainable media for multicomponent sulfonylation: an efficient strategy to synthesize (hetero)aryl sulfones

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(3), P. 1387 - 1392

Published: Jan. 1, 2024

A green and sustainable multicomponent sulfonylation starting from boronic acids, K 2 S O 5 halides has been developed using a deep eutectic solvent (DES) as reaction medium.

Language: Английский

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Chemodivergent dearomatization of benzene-linked O-oxime esters via EnT-induced radical cross-coupling

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Radical-mediated dearomatization strategies offer a blueprint for building value-added and synthetically valuable three-dimensional skeletons from readily available aromatic starting materials.

Language: Английский

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Radical-mediated sulfonylation relay of alkyl alkynes/alkenes and electron-deficient alkenes to access vinyl and alkyl sulfones

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A radical-mediated sulfonylation relay of alkyl alkynes/alkenes with electron-deficient alkenes using Na 2 S O 4 as a linker is developed to synthesize highly selective ( Z )-vinyl and sulfones under metal-free catalyzed system.

Language: Английский

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Visible light-mediated dearomative spirocyclization/imination of nonactivated arenes through energy transfer catalysis

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: April 16, 2025

Abstract Aromatic compounds serve as key feedstocks in the chemical industry, typically undergoing functionalization or full reduction. However, partial reduction via dearomative sequences remains underexplored despite its potential to rapidly generate complex three-dimensional scaffolds and existing strategies often require metal-mediated multistep processes suffer from limited applicability. Herein, a photocatalytic radical cascade approach enabling difunctionalization through selective spirocyclization/imination of nonactivated arenes is reported. The method employs bifunctional oxime esters carbonates introduce multiple functional groups single step, forming spirocyclic motifs iminyl functionalities N–O bond cleavage, hydrogen-atom transfer, addition, spirocyclization, radical-radical cross-coupling. reaction constructs up four bonds (C−O, C−C, C−N) simple starting materials. Its broad applicability demonstrated on various substrates, including pharmaceuticals, it compatible with scale-up under flow conditions, offering streamlined synthesizing highly decorated frameworks.

Language: Английский

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Photosensitized Imino-Sulfamoylation of Alkenes with Oxime Carbamates

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: May 1, 2025

In this study, we have devised a strategy that employs oxime carbamate as bifunctional diamination reagent in combination with SO2 to realize imino-sulfamoylation of alkenes. This protocol is characterized by its mild conditions, operational simplicity, and metal-free nature, while demonstrating broad functional group tolerance for Furthermore, the application method provides an accessible route diverse range β-amino sulfonamide derivatives.

Language: Английский

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Functionalization of Cubane Formation of C−C and C−Heteroatom Bonds

Helvetica Chimica Acta, Journal Year: 2024, Volume and Issue: 107(2)

Published: Feb. 1, 2024

Abstract Functionalized cubanes are attractive scaffolds for medicinal chemists as they bioisosteres of benzene rings. The replacement a ring by cubane, in bioactive compound, can have beneficial effect on the biological activity such compound. Thus, design new molecular cubyl building blocks is importance. In this review, we will focus functionalization creating C−C, C−heteroatom bonds e. g. C−N, C−O, C−B, C−P and C−S bonds. Different methods reported involving organometallics, radicals, ionic species. Mechanisms included when relevant.

Language: Английский

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