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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Photocatalytic Unsymmetrical Diamination of Styrenes, Indoles, and Benzofurans Facilitated by Benzotriazolyl and Iminyl Radicals

Organic Letters, Год журнала: 2024, Номер 26(2), С. 559 - 564

Опубликована: Янв. 9, 2024

Utilizing energy transfer catalysis, this research employed the bifunctional reagents benzotriazole carboxylic acid oxime esters to simultaneously generate and imine radicals. The synthesis of two distinct C–N bonds in a single conversion is showcased through radical addition radical–radical cross-coupling processes between ester olefins. This process facilitates intermolecular two-component unsymmetrical diamination reaction Using approach, more than 40 benzotriazole-containing molecules were successfully synthesized using styrene, indole, benzofuran as acceptors, with yields ranging from moderate excellent.

Язык: Английский

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Recent Advances in Visible Light‐Mediated Radical Fluoro‐alkylation, ‐alkoxylation, ‐alkylthiolation, ‐alkylselenolation, and ‐alkylamination

The Chemical Record, Год журнала: 2023, Номер 23(9)

Опубликована: Май 22, 2023

Abstract In the last few years, many reagents and protocols have been developed to allow for efficient fluorofunctionalization of a diverse set scaffolds ranging from alkanes, alkenes, alkynes, (hetero)arenes. The concomitant rise organofluorine chemistry visible light‐mediated synthesis synergistically expanded fields mutually benefitted developments in both fields. this context, light driven formations radicals containing fluorine major focus discovery new bioactive compounds. This review details recent advances progress made fluoroalkylation heteroatom centered radical generation.

Язык: Английский

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Photocatalytic Sulfonyl Peroxidation of Alkenes via Deamination of N-Sulfonyl Ketimines

Organic Letters, Год журнала: 2024, Номер 26(9), С. 1920 - 1925

Опубликована: Фев. 22, 2024

A photocatalytic three-component sulfonyl peroxidation of alkenes with N-sulfonyl ketimines and tert-butyl hydroperoxide is reported. The reaction takes place via the photoinduced EnT process, which allows efficient synthesis a variety β-peroxyl sulfones under mild conditions in absence transition metal catalyst. downstream derivatizations peroxides were also performed. Furthermore, utility this protocol was manifested by 11β-HSD1 inhibitor antiprostate cancer drug bicalutamide.

Язык: Английский

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Photosensitized 1,2-Difunctionalization of Alkenes to Access β-Amino Sulfonamides

Organic Letters, Год журнала: 2024, Номер 26(10), С. 2108 - 2113

Опубликована: Март 5, 2024

A metal-free photosensitized 1,2-imino-sulfamoylation of olefins by employing a tailor-made sulfamoyl carbamate as the difunctionalization reagent has been established. This protocol exhibits versatility across broad substrate scope, including aryl and aliphatic alkenes, leading to synthesis diverse β-imino sulfonamides in moderate good yields. method is characterized its reaction system, mild conditions, excellent regioselectivity, high atom economy, serving promising platform for preparation β-amino sulfonamide-containing molecules, particularly context drug discovery.

Язык: Английский

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Chemo-divergent Cyano Group Migration: Involving Elimination and Substitution of the Key α-Thianthrenium Cyano Species

Organic Letters, Год журнала: 2023, Номер 25(36), С. 6633 - 6637

Опубликована: Сен. 6, 2023

Herein, we report a light-driven, radical-type cyano migration in the absence of photocatalyst, enabling chemo-divergent synthesis (Z)-alkenyl nitriles and ketones. Trifluoromethyl thianthrenium salt (TT–CF3+OTf–) plays multiple roles: (a) absorbing light to generate trifluoromethyl radicals initiate reaction (b) forming α-thianthrenium species by situ capture TT• +. (Z)-Alkenyl were formed through elimination salts, aryl ketones obtained via nucleophilic substitution salts.

Язык: Английский

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Photo-induced imino functionalizations of alkenes via intermolecular charge transfer

Chemical Science, Год журнала: 2023, Номер 14(40), С. 11170 - 11179

Опубликована: Янв. 1, 2023

A catalyst-free photosensitized strategy has been developed for regioselective imino functionalizations of alkenes via the formation an EDA complex. This photo-induced protocol facilitates construction structurally diverse β-imino sulfones and vinyl in moderate to high yields. Mechanistic studies reveal that reaction is initiated with intermolecular charge transfer between oximes sulfinates, followed by fragmentation generate a persistent iminyl radical transient sulfonyl radical. also features excellent regioselectivity, broad functional group tolerance mild conditions. The late stage functionalization natural product derived compounds total synthesis some bioactive molecules have demonstrated highlight utility this protocol. Meanwhile, compatibility different donors proved generality strategy.

Язык: Английский

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Photocatalytic vinyl radical-mediated multicomponent 1,4-/1,8-carboimination across alkynes and olefins/(hetero)arenes

Science China Chemistry, Год журнала: 2023, Номер 67(2), С. 558 - 567

Опубликована: Сен. 27, 2023

Язык: Английский

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Visible-Light-Promoted Intermolecular β-Acyl Difunctionalization of Alkenes via Oxidative Radical-Polar Crossover

Organic Letters, Год журнала: 2023, Номер 25(45), С. 8067 - 8071

Опубликована: Ноя. 8, 2023

A visible-light-induced β-acyl difunctionalization of alkenes with acyl oxime esters and various nucleophiles was developed to achieve molecular complexity from readily available raw materials via oxidative radical-polar crossover. variety nucleophiles, including NH-sulfoximines, indoles, indazole, trimethoxybenzene, were all effectively applicable the sustainable reaction system. The novel synthetic strategy features mild conditions, a broad substrate scope (39 examples), easy scale-up, excellent regioselectivity.

Язык: Английский

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