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

ACS Catalysis, Год журнала: 2025, Номер 15(3), С. 1854 - 1941

Опубликована: Янв. 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

Язык: Английский

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Photocatalytic Thio/Selenosulfonylation–Bicyclization of Indole-Tethered 1,6-Enynes Leading to Substituted Benzo[c]pyrrolo[1,2,3-lm]carbazoles

Organic Letters, Год журнала: 2024, Номер 26(18), С. 3828 - 3833

Опубликована: Апрель 29, 2024

The photocatalyzed radical-triggered thio/selenosulfonylation–bicyclization of indole-tethered 1,6-enynes has been established for the first time, enabling synthesis various previously unreported thio/selenosulfonylated benzo[c]pyrrolo[1,2,3-lm]carbazoles with moderate to good yields under mild conditions. reaction pathway was proposed, consisting energy transfer, homolytic cleavage, radical addition, 5-exo-dig, coupling, and a Mallory cascade. This approach exhibits wide substrate compatibility excellent tolerability toward functional groups is characterized by its remarkable efficiency in both bond formation annulation.

Язык: Английский

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Recent advances in the dichalcogenation reactions of unsaturated compounds via double functionalization

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(19), С. 4972 - 5027

Опубликована: Янв. 1, 2023

This review comprehensively summarizes the dichalcogenative functionalization of unsaturated compounds over past decade. The scopes, limitations and detailed reaction mechanisms are also discussed.

Язык: Английский

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Controllable Construction of Vinyl Sulfones and β‐Keto Selenosulfones via Selective Oxidative Sulfonylation of Alkenes

Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(12), С. 1367 - 1372

Опубликована: Фев. 23, 2024

Comprehensive Summary The selective oxidative sulfonylation of alkenes with selenium sulfonate depended on the reaction conditions. electrochemical C—H proceeded smoothly to afford ( E )‐vinyl sulfones good selectivity in an undivided cell without external oxidant. While aerobic trifunctionalization occurred presence KI air, which provides β ‐keto selenosulfones via formation C—O, C—S, and C—Se bonds one‐pot. Following control experiments, a plausible mechanism is proposed rationalize experimental results.

Язык: Английский

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Recyclable Iridium Catalyst Supported on Porous Organic Polymer for Acceptorless Dehydrogenative Silylation: Synthesis of Ring‐Fused Oxasilacycles

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(8), С. 1763 - 1769

Опубликована: Март 1, 2024

Abstract The direct conversion of specific C−H bonds to C−Si in alkanes or aromatics via catalytic methods has attracted growing research interest. Herein, we report the preparation a new iridium catalyst supported on naphthyridine‐based porous organic polymer and its successful application dehydrogenative silylation 2‐arylphenols alcohol hydrosilanes access ring‐fused oxasilacycles. synthetic method exhibits broad substrate scope good functional group compatibility while avoiding use hydrogen acceptors. In addition, this could be easily recovered from reaction system reused for at least seven times without apparent deactivation. This provides insights further design heterogeneous nanocatalysts contributes synthesis silicon‐substituted molecules.

Язык: Английский

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Stabilized Carbon‐Centered Radical‐Mediated Carbosulfenylation of Styrenes: Modular Synthesis of Sulfur‐Containing Glycine and Peptide Derivatives

Advanced Science, Год журнала: 2024, Номер 11(29)

Опубликована: Июнь 9, 2024

Abstract Sulfur‐containing amino acids and peptides play critical roles in organisms. Thiol‐ene reactions between the thiol residues of L ‐cysteine alkenyl fragments designed coupling partners serve as primary tools for constructing C─S bonds synthesis unnatural sulfur‐containing acid derivatives. These are favored due to preference hydrogen transfer from β‐sulfanyl carbon radical intermediates. In this paper, study proposes utilizing carbon‐centered radicals stabilized by capto‐dative effect, generated under photocatalytic conditions N –aryl glycine The aim is compete with hydrogen, enabling C─C bond formation radicals. This protocol robust presence air water, offers significant potential a modular efficient platform synthesizing modifying peptides, particularly abundant disulfides styrenes.

Язык: Английский

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Simultaneous Preparation of Sulfides/Selenides and Sulfones via Synergistic Nickel-Catalyzed Reductive Coupling and S_N2 Reaction

Organic Letters, Год журнала: 2023, Номер 25(51), С. 9207 - 9212

Опубликована: Дек. 19, 2023

Sulfone compounds and thioether are two highly valuable classes of compounds, but it is challenging to prepare sulfone simultaneously efficiently. Here we report that sulfides/selenides sulfones can be obtained using allyl bromide/benzyl bromide-activated alkyl bromides thiosulfonates/selenosulfonates a nickel-catalyzed reductive coupling SN2 synergistic strategy, which characterized by excellent atom step economy, mild reaction conditions, broad functional group compatibility, yields.

Язык: Английский

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Recent Progress in Synthesis of Organosilanes Driven by Visible-Light

Chinese Journal of Organic Chemistry, Год журнала: 2023, Номер 43(10), С. 3454 - 3454

Опубликована: Янв. 1, 2023

Silahydrocarbons are often encountered in pharmaceuticals and material chemistry.In comparison with all-carbon parent compounds, carbon/silicon switch generally endows the corresponding compounds different biological activity physical-chemical properties.In this review, methods strategies of synthesis organosilanes by photoredox recent years reviewed, reaction mechanisms limitations discussed.

Язык: Английский

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Ni-catalyzed highly regio- and stereo-selective diborylative cyclization of 1,6-enynes with diboron reagent

Science China Chemistry, Год журнала: 2023, Номер 67(3), С. 981 - 989

Опубликована: Дек. 5, 2023

Язык: Английский

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3‐Amido‐benzo[b]silines: Straightforward Modular 2‐Step Synthesis and Photophysical Properties

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(10), С. 2324 - 2333

Опубликована: Апрель 3, 2024

Abstract In this manuscript we report the synthesis of 3‐amido‐benzo[ b ]silines thanks to a 2‐step strategy involving 3‐component silylformylation ynamides followed by Friedel‐Crafts cyclization/isomerizing dehydration domino sequence. This reaction is tolerant various structural variations and has allowed us synthesize library diversely substituted silacycles with yields from 33 85%. We also studied fluorescence properties these compounds which show similarities recognized probes such as Si‐Rhodamine for example.

Язык: Английский

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