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

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1854 - 1941

Published: Jan. 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

Language: Английский

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Electron Donor–Acceptor Complex Enabled Cyclization/Sulfonylation Cascade of N-Heterocycles with Thianthrenium Salts

Organic Letters, Journal Year: 2024, Volume and Issue: 26(31), P. 6652 - 6657

Published: July 26, 2024

We report a visible-light-promoted cyclization/sulfonylation cascade of N-heterocycles with thianthrenium salts using DABSO as the SO2 surrogate. This method features excellent functional group tolerance, wide substrate scope, and late-stage elaboration bioactive relevant molecules. Mechanistic investigations reveal that photoactive electron donor–acceptor (EDA) complexes between DABCO are capable generation aryl radicals, which induce following insertion by attacking DABSO, thus triggering key radical cyclization step.

Language: Английский

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Recent Progress in C–S Bond Formation via Electron Donor-Acceptor Photoactivation

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review summarizes recent progress in EDA complex-promoted C–S bond formation using various sulfur-containing substrates under mild conditions via visible light irradiation.

Language: Английский

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Four-Component Radical 1,2-Selenosulfonylation of Allenes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(27), P. 5705 - 5712

Published: June 27, 2024

Selenosulfones, as pivotal pharmaceutical molecule frameworks, have become a research hotspot in modern organic synthesis due to their vital need for efficient preparation. Herein, we developed an iron-catalyzed four-component controllable radical tandem reaction of allenes involving cycloketone oxime esters, 1,4-diazabicyclo[2.2.2]octane bis(sulfur dioxide) adduct (DABSO), and diphenyl diselenides the complex selenosulfones. This is first case achieving 1,2-selenosulfonylation via process, wherein precise control rates polarity matching enhance high regioselective conversion. The conditions are ecofriendly mild with step-efficiency by forming two new C–S bonds one C–Se bond pot. Moreover, can be achieved replacing esters aryldiazonium tetrafluoroborates this system.

Language: Английский

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Divergent Reactivity of Iminyl Radicals in Four Interrupted Pathways for the Synthesis of Cyclic/Acyclic Ketones and N-Heterocycles from Vinyl Azides and Phenylacetic Acids

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(18), P. 13128 - 13136

Published: Sept. 11, 2024

Herein, we report the Ag-catalyzed substrate-controlled interrupted radical pathways of iminyl radical. The benzylic groups played a crucial role in pathway selection involving series dimerization and hydrolysis, 1,5-H shift followed by cascade cyclization, direct N-(sp

Language: Английский

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Bifunctionalization of α-Bromophenone: An Access to Functionalized β-Keto Thiosulfones

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 12, 2024

A simple and high-yielding strategy to produce a variety of β-keto sulfides using asymmetrical symmetrical thiosulfonates with ketones under mild conditions is reported. It was found that the various substituted compounds, both electron-withdrawing electron-donating substituents, afforded wide range thiosulfones (α-thioaryl-β-keto sulfones) in moderate high yields. The transformations were reliable at gram-scale, thus illustrating their efficiency practicality. plausible mechanism for protocol also proposed.

Language: Английский

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Facile synthesis of 2-substituted benzofurans by intermolecular [3+2] cycloaddition of benzoquinone and vinyl azides under air

Tetrahedron, Journal Year: 2024, Volume and Issue: 167, P. 134277 - 134277

Published: Sept. 21, 2024

Language: Английский

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Oxyphosphorodithiolation of Vinyl Azides with P₄S₁₀ and Alcohols Leading to β-Keto Phosphorodithioates

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(24), P. 18384 - 18392

Published: Dec. 10, 2024

A simple strategy for the synthesis of β-keto phosphorodithioates has been developed through direct oxyphosphorodithiolation vinyl azides with P

Language: Английский

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