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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Copper-Catalyzed Radical Relay 1,3-Carbocarbonylation across Two Distinct C═C Bonds

Organic Letters, Год журнала: 2024, Номер 26(15), С. 3014 - 3019

Опубликована: Март 28, 2024

The radical relay provides an effective paradigm for intermolecular assembly to achieve functionalization across remote chemical bonds. Herein, we report the first 1,3-carbocarbonylation of α-carbonyl alkyl bromides two separate C═C reaction is highly chemo- and regioselective, with C(sp3)–C(sp3) bonds one C═O bond formed in a single orchestrated operation. In addition, synthesis method under mild conditions using inexpensive copper as catalyst allows facile access structurally diverse products. plausible mechanism investigated through series control experiments, including trapping, clock critical intermediate 18O labeling experiment.

Язык: Английский

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Visible-light-induced photocatalyst-free activation of alkynyl triflones for trifluoromethylalkynylation of unactivated 1,6-dialkenes

Green Chemistry, Год журнала: 2023, Номер 25(15), С. 6009 - 6013

Опубликована: Янв. 1, 2023

A visible-light-induced trifluoromethylalkynylation of 1,6-dialkenes was developed under transition-metal-free and photocatalyst-free conditions, enabling the construction three C–C bonds in a single preparation step.

Язык: Английский

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Advances in the Synthesis of α-Trifluoromethyl Ketones and Their Application via Defluorinative Reactions

Chinese Journal of Organic Chemistry, Год журнала: 2025, Номер 45(1), С. 86 - 86

Опубликована: Янв. 1, 2025

Язык: Английский

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Alkynyl Radicals, Myths and Realities

JACS Au, Год журнала: 2025, Номер 5(2), С. 448 - 465

Опубликована: Фев. 6, 2025

This Perspective deals with the organic chemistry of alkynyl radicals, a species that is ultimately still little known in synthetic community. Starting first observations and characterizations radicals generated by various methodologies gas phase, we then particularly turned our attention to implications these highly reactive intermediates synthesis materials science. Mechanistic considerations have been provided, particular, for key steps generating which are mainly based on photochemical or thermal activation single electron transfer processes. should serve as roadmap chemist order plan more reliably alkynylation reactions radicals.

Язык: Английский

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Sequential Ring Opening/In Situ SO₂-Capture/Alkynylation of Cyclopropanols with Alkynyl Triflones Initiated by Energy Transfer

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(11), С. 7656 - 7661

Опубликована: Май 15, 2024

A visible-light-triggered ring opening/in situ SO2-capture/alkynylation sequence of cyclopropyl alcohols with alkynyl triflones using 4CzIPN as a triplet energy transfer photocatalyst is herein described. This metal-free protocol provides straightforward and atom-economical approach to alkynyl-substituted γ-keto sulfones broad scope substituents. In this transformation, could be used both radical acceptors SO2 donors. Preliminary experimental mechanistic studies synthetic utility are also demonstrated.

Язык: Английский

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Stereoselective synthesis of α-glycosyl azides: allyl glycosyl sulfones as radical precursors

Chemical Communications, Год журнала: 2024, Номер 60(49), С. 6288 - 6291

Опубликована: Янв. 1, 2024

We introduce a radical reaction for the stereoselective synthesis of α-glycosyl azides using bench-stable allyl glycosyl sulfones as donor.

Язык: Английский

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Photocatalytic [2+2+m] Cyclization of 2‐Cyanoaryl Acrylamides with 2‐Bromocarbonyls Involving C(sp³)−H Functionalization

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(24), С. 4513 - 4519

Опубликована: Окт. 31, 2023

Abstract An oxidant‐free photocatalytic [2+2+m] cyclization of 2‐cyanoaryl acrylamides with 2‐bromocarbonyls is reported, enabling the assembly biologically important N‐heterocycle‐fused quinolinones including benzo[1,6]naphthyridinones and pyrrolo[3,2‐ c ]‐quinolines. This protocol proceeds through a radical relay pathway alkene difunctionalization along an intramolecular cyano insertion subsequent site‐specific functionalization inert C( sp 3 )−H bond enabled by cyano‐derived iminyl radical‐mediated 1,n‐hydrogen atom transfer. Notably, this transformation selectively formed two distinct C−C bonds, one C−N bond, quaternary carbon center in one‐pot procedure.

Язык: Английский

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Visible-Light-Mediated Trifluoromethylalkynylation of Unactivated 1,6-Dialkenes

Chinese Journal of Organic Chemistry, Год журнала: 2023, Номер 43(10), С. 3669 - 3669

Опубликована: Янв. 1, 2023

Plausible reaction mechanism

Язык: Английский

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