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

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(43), С. 23814 - 23823

Опубликована: Окт. 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.

Язык: Английский

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Direct C(sp3)-H functionalization with aryl and alkyl radicals as intermolecular hydrogen atom transfer (HAT) agents

Chemical Communications, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Recent years have witnessed the emergence of direct intermolecular C(sp

Язык: Английский

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Photosensitized Imino-Sulfamoylation of Alkenes with Oxime Carbamates

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Май 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.

Язык: Английский

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Nitrogen–Nitrogen Radical Coupling-Enabled Precise Difunctionalization of Carbon–Nitrogen Double Bonds

Organic Letters, Год журнала: 2024, Номер 26(46), С. 9931 - 9936

Опубликована: Ноя. 11, 2024

In this study, we have developed a metal-free, photoinduced energy transfer strategy for the efficient difunctionalization of carbon-nitrogen double bonds (C═N). Utilizing oxime ester-based bifunctional reagents, achieved direct radical C═N through nitrogen-nitrogen coupling, with over 35 examples and yields up to 96%. This method exhibits broad substrate scope, being compatible variety carboxylic acids biologically active molecules, thus offering novel approach heteroatom-containing unsaturated in synthetic chemistry.

Язык: Английский

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Photoinduced EnT-Mediated Sulfonamidylimination of Alkenes and (Hetero)arenes with Iminophenylacetic Acids Oxime Esters

Chemical Communications, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Sulfonamidyl radicals are generated via photoinduced EnT and applied for the diamination of alkenes (hetero)arenes.

Язык: Английский

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Recent Advances in Strategies for Halide Atom Transfer (XAT) and Their Applications

Chinese Journal of Organic Chemistry, Год журнала: 2024, Номер 44(6), С. 1733 - 1733

Опубликована: Янв. 1, 2024

Язык: Английский

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Photocatalyzed Imino-Difluoromethylation of Alkenes with Bifunctional Oxime Esters

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(18), С. 13585 - 13594

Опубликована: Сен. 11, 2024

Herein, we report a simple and versatile difluoromethylene-imide reaction in which series of olefins can undergo difluoromethylenimine under photocatalytic conditions through an energy transfer (EnT) process. The has mild wide range applicability. We successfully synthesized 27 molecules containing difluoromethylene units, featuring easily accessible starting materials operational simplicity.

Язык: Английский

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Photoinduced amination of iodoalkanes enabled by bifunctional O-benzoyl oxime

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(7), С. 1949 - 1954

Опубликована: Янв. 1, 2024

A photo-induced amination strategy that facilitates the transformation of iodoalkanes and bifunctional O -benzoyl oxime into alkyl amines is herein reported.

Язык: Английский

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Photosensitized Three-Component Carboimination of Alkenes Based on the Relay of Oxy Radicals to Carbon Radicals

Organic Letters, Год журнала: 2024, Номер 26(43), С. 9263 - 9268

Опубликована: Окт. 21, 2024

Here, we present a metal-free photosensitized three-component reaction for the carboimination of alkenes based on oxime carbonates. Homolysis carbonates via light-mediated energy transfer enables simultaneous generation iminyl radicals and alkoxycarbonyloxyl radicals. The alkoxy can act as an effective hydrogen atom reagent, abstracting atoms from alkanes aldehydes, silanes, phosphine oxide. This strategy exhibits broad functional group tolerance under mild conditions, further broadening diversity alkene carboimination.

Язык: Английский

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