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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Access to Polysulfides through Photocatalyzed Dithiosulfonylation

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(25)

Опубликована: Апрель 15, 2023

Abstract In this study, we outline a general method for photocatalyzed difunctionalization of alkenes, diene, alkynes, 1,3‐enynes, and [1.1.1]propellane using dithiosulfonate reagents (ArSO 2 ‐SSR) with improved atom economy. Both “ArSO ‐” “‐SSR” on the are transferred under mild conditions broad substrate scope, high stereoselectivity, complete regioselectivity. Significantly, resulting dithiosulfonylated styrene is practical nucleophilic disulfuration reagent, reacting variety electrophiles efficiently. reactions can be conducted gram scale, rendering approach highly valuable.

Язык: Английский

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“Alkene-to-Alkene” Difunctionalization of Enaminones for the Synthesis of Polyfunctionalized Alkenes by Transition-Metal-Free C–H and C–N Bond Transformation

Organic Letters, Год журнала: 2023, Номер 25(47), С. 8451 - 8456

Опубликована: Ноя. 16, 2023

The three-component reactions of enaminones, disulfides, and alcohols for the synthesis polyfunctionalized alkenes have been realized via C-H C-N bond transformation on enaminones. proceed in a novel "alkene-to-alkene" difunctionalization mode without using any transition metal. application alkene products divergent sulfenyl heteroaryls, including sulfenylated pyrazoles, pyrimidines, isoxazoles, simple annulation has also verified.

Язык: Английский

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Photoinduced Regioselective Sulfonylsulfination of Alkenes

ACS Catalysis, Год журнала: 2024, Номер 14(5), С. 3664 - 3674

Опубликована: Фев. 21, 2024

Regioselective 1,2-dichalcogenation of alkenes has attracted significant attention in modern organic synthetic chemistry. While there are a plethora methods to access alkene dichalcogenated architectures, sulfonylsulfination is extremely challenging due the inherent characteristics sulfur atom. Herein, multicomponent fragment coupling alkenes, sulfinates, and DABSO was developed construct densely functionalized sulfonylsulfinated products, which otherwise access, with broad substrate scope group tolerance under mild operationally simple conditions, using an inexpensive 100–1000 ppm photocatalyst. In addition, protocol applied late-stage functionalization complex molecules, obtained products were converted into diverse downstream transformations demonstrate their potential. Experimental theoretical mechanistic investigations suggest that these reactions proceed through sequential sulfonyl sulfinyl oxygen radical mutual radical–polar crossover coupling. This strategy provides previously inaccessible good-to-high regio- stereoselectivity, along opening up unexplored directions.

Язык: Английский

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E‐Selective Radical Difunctionalization of Unactivated Alkynes: Preparation of Functionalized Allyl Alcohols from Aliphatic Alkynes

Advanced Science, Год журнала: 2024, Номер 11(16)

Опубликована: Фев. 13, 2024

Abstract Radical difunctionalization of aliphatic alkynes provides direct access to valuable multi‐substituted alkenes, but achieving a high level chemo‐ and stereo‐control remains formidable challenge. Herein novel photoredox neutral alkyne di‐functionalization is reported through functional group migration followed by radical‐polar crossover energy transfer‐enabled stereoconvergent isomerization alkenes. In this sequence, hydroxyalkyl an aryl are incorporated concomitantly into alkyne, leading diversely functionalized E‐allyl alcohols. The scope noteworthy, the reaction tolerates containing hydrogen donating C─H bonds that prone intramolecular atom transfer. protocol features broad compatibility, product diversity, exclusive stereoselectivity, thus providing practical strategy for elusive radical unactivated alkynes.

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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Electrocatalytic Multicomponent Cascade Cross‐Coupling for the Synthesis of Chalcogenosulfonates

Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(17), С. 2049 - 2055

Опубликована: Май 7, 2024

Comprehensive Summary An electrocatalytic multicomponent cascade cross‐coupling for the synthesis of chalcogenosulfonates has been established. This approach does not require use transition metals, acids, and external oxidants. The gentle conditions tolerance to a wide variety functional groups permit derivatization complex indoles.

Язык: Английский

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Cobalt-Catalyzed Chemoselective and Divergent Synthesis of Vinylsilanes through Hydrosilylation of Acetylene

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4429 - 4440

Опубликована: Фев. 28, 2025

Язык: Английский

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Bifunctional two-carbon reagent made from acetylene via 1,2-difunctionalization and its applications

Science China Chemistry, Год журнала: 2024, Номер 67(3), С. 936 - 944

Опубликована: Янв. 8, 2024

Язык: Английский

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Photo-induced decarboxylative C-S bond formation to access sterically hindered unsymmetric S-alkyl thiosulfonates and SS-alkyl thiosulfonates

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Авг. 25, 2024

Due to the high reactivity and versatility of benzenesulfonothioates, significant advancements have been made in constructing C-S bonds. However, there are certain limitations synthesis S-thiosulfonates SS-thiosulfonates, especially when dealing with substantial steric hindrance, which poses a challenge. Herein, we present an innovative approach for assembling unsymmetric SS-thiosulfonates through integration dual copper/photoredox catalysis. Moreover, also realized one-pot strategy by directly using carboxylic acids as raw materials in-situ activation them access without further purification presynthesis NHPI esters. The envisaged utilization these reagents poised pioneer pathway fabricating versatile spectrum mono-, di-, polysulfide compounds. Furthermore, they introduce class potent sulfenylating reagents, empowering intricate unsymmetrical disulfides that were previously challenging access. conventional method synthesizing thioether compounds typically relies on thiol, disulfide, sulfinyl halide initial substances, suffering from strong odors, limited availability, issues. Here, authors catalysis

Язык: Английский

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