Photoredox-Catalyzed and Copper(II) Salt-Assisted Radical Addition/Hydroxylation Reaction of Alkenes, Sulfur Ylides, and Water

ACS Catalysis, Год журнала: 2022, Номер 12(6), С. 3279 - 3285

Опубликована: Фев. 25, 2022

A visible light-driven photoredox-catalyzed and copper(II)-assisted three-component radical addition/hydroxylation reaction of alkenes, sulfur ylides, water is reported. This process shows broad substrate scope high functional group tolerance, with respect to both readily available ylides providing high-yielding practical access valuable γ-hydroxy carbonyl compounds. Key the success controlled generation α-carbonyl carbon radicals from via sulfonium salts by a visible-light-driven proton-coupled electron transfer (PCET) strategy in mixture 2,2,2-trifluoroethanol/CH2Cl2. Addition Cu(TFA)2·H2O helps accelerate radical-cation crossover improve efficiency. Mechanistic studies suggest that hydroxy moiety products stems water. study also builds up platform for further investigation into synthetic chemistry ylides.

Язык: Английский

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Dual Nickel/Photoredox-Catalyzed Arylsulfonylation of Allenes

Organic Letters, Год журнала: 2024, Номер 26(24), С. 5074 - 5081

Опубликована: Июнь 10, 2024

The nickel/photoredox dual catalysis system is an efficient conversion platform for the difunctionalization of unsaturated hydrocarbons. Herein, we disclose first nickel/photoredox-catalyzed intramolecular 1,2-arylsulfonylation allenes, which can accurately construct a C(sp2)–C(sp2) bond and C(sp3)–S bond. reaction exhibits excellent chemoselectivity regioselectivity, allowing modular conformations diverse series 3-sulfonylmethylbenzofuran derivatives. Control experiments showed that bipyridine ligand crucial formation stable σ-alkyl nickel intermediate, providing possibility sulfonyl radical insertion. Meanwhile, electrophilic facilitates further oxidative addition intermediate inhibits with allenes. In addition, control experiments, cyclic voltammetry tests, Stern–Volmer density functional theory calculations afford evidence Ni(0)/Ni(I)/Ni(II)/Ni(III) pathway in this 1,2-arylsulfonylation.

Язык: Английский

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Recent advances in dual photoredox/nickel catalyzed alkene carbofunctionalised reactions

Chemical Communications, Год журнала: 2024, Номер 60(68), С. 8946 - 8977

Опубликована: Янв. 1, 2024

Alkene carbofunctionalization reactions have great potential for synthesizing complex molecules and constructing structures in natural products medicinal chemistry. Recently, dual photoredox/nickel catalysis has emerged as a novel strategy alkene carbofunctionalization. Nickel offers numerous advantages over other transition metals, such cost-effectiveness, abundance, low toxicity, moreover, it many oxidation states. catalysts exhibit excellent catalytic activity photoredox/transition metal catalysis, facilitating the formation of carbon-carbon or carbon-heteroatom bonds organic transformations. This review highlights latest advancements photoredox/nickel-catalyzed carbofunctionalizations includes literature published from 2020 to 2024.

Язык: Английский

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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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Recent Advances in Photoredox-Catalyzed Difunctionalization of Alkenes

Catalysts, Год журнала: 2023, Номер 13(7), С. 1056 - 1056

Опубликована: Июнь 30, 2023

Alkenes and their related analogs are ideal starting materials for organic synthesis, the selective difunctionalization of alkenes, which allows simultaneous introduction two neighboring bonds, has gained considerable attention in recent years. In particular, photoredox-catalyzed alkenes also been accomplished, regarded as an increasingly powerful tool synthesis miscellaneous interesting molecular scaffolds environmentally benign economical manner. Several exquisite strategies have developed to facilitate this transformation, such photosensitizer-catalyzed redox reactions, electron donor-acceptor (EDA) complexes-mediated photoreactions, atom transfer radical addition (ATRA) reactions. This literature review briefly describes most key progress on 1,2-difunctionalization various structurally diverse including 1,2-dicarbofunctionalization, 1,2-carboheterofunctionalization, 1,2-diheterofunctionalization, with a special emphasis mechanistic details.

Язык: Английский

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Photoredox/Nickel Dual Catalysis-Enabled Modular Synthesis of Arylallyl Alcohols with Acetylene as the Two-Carbon Synthon

ACS Catalysis, Год журнала: 2023, Номер 13(4), С. 2422 - 2431

Опубликована: Фев. 2, 2023

Arylallyl alcohols are commonly found in natural products and drug molecules. The traditional syntheses primarily rely on two-component reactions using presynthesized alkenes. Herein, we report a photoredox/nickel dual-catalyzed three-component cross-coupling reaction, which enables the rapid synthesis of arylallyl with acetylene as two-carbon (C2) synthon. In this aryl halide carbonyl compound were sewn together linker. A series synthesized an atmosphere (1 atm). This method features broad substrate scopes, good functional group tolerance, high Z-selectivity. addition to intermolecular difunctionalization acetylene, reaction is also amenable intramolecular ring formation, giving highly valuable indenols indanones. mechanistic investigation indicates that alkenylnickel key intermediate. intermediate can be considered alternative alkenyl Grignard reagent but better compatibility. With step, several important molecules including have been prepared.

Язык: Английский

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Copper‐Catalyzed Chemo‐ and Enantioselective Radical 1,2‐Carbophosphonylation of Styrenes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(13)

Опубликована: Фев. 1, 2023

The copper-catalyzed enantioselective radical difunctionalization of alkenes from readily available alkyl halides and organophosphorus reagents possessing a P-H bond provides an appealing approach for the synthesis α-chiral phosphorus compounds. major challenge arises easy generation P-centered P-H-type reagent its facile addition to terminal side alkenes, leading reverse chemoselectivity. We herein disclose 1,2-carbophosphonylation styrenes in highly chemo- manner. key success lies not only implementation dialkyl phosphites with strong dissociation energy promote desired chemoselectivity but also utilization anionic chiral N,N,N-ligand forge C(sp3 )-P bond. developed Cu/N,N,N-ligand catalyst has enriched our library single-electron transfer catalysts transformations.

Язык: Английский

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Nitrative Difunctionalization of Alkenes via Cobalt-Mediated Radical Ligand Transfer and Radical-Polar Crossover Photoredox Catalysis

ACS Catalysis, Год журнала: 2023, Номер 13(24), С. 16136 - 16147

Опубликована: Дек. 1, 2023

Herein, we report the rational design of a modular dual photoredox and cobalt catalysis paradigm for difunctionalization unsaturated hydrocarbons, unlocking synthesis valuable but challenging 1,2-halonitroalkane substrate class. The protocol relies on use redox-active organic nitrating reagent N-nitrosuccinimide as source nitryl radicals cobalt-mediated radical ligand transfer (RLT) methodology to form carbon–halogen bond. This synergistic cooperation between photocatalyst high-valence metal center occurs under mild reaction conditions is capable delivering 1,2-chloronitro- 1,2-bromonitroalkanes in single chemical operation while exhibiting high functional-group tolerance exclusive regioselectivity variety olefins. Mechanistic studies based both experimental spectroscopic analysis provided insights into nature this catalytic halo-nitration process including evidence halogen catalyst. Furthermore, employing net-neutral radical/polar crossover (RPC) approach cobalt-free allowed us accommodate external protic nucleophiles, thiols, alcohols, acids, and, notably, substituted amines. Highly functionalized olefin scaffolds also successfully underwent nitrative difunctionalization, demonstrating viability these protocols late-stage functionalization bioactive molecules.

Язык: Английский

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Lewis Acid Promoted Vicinal Oxytrifluoromethylselenolation of Alkenes

Organic Letters, Год журнала: 2023, Номер 25(18), С. 3210 - 3215

Опубликована: Апрель 28, 2023

Herein, we have developed a metal-free, Lewis acid promoted vicinal oxytrifluoromethylselenolation of alkenes using trifluoromethyl selenoxides as electrophilic trifluoromethylselenolation reagents and alcohols nucleophiles. With less steric good nucleophilic solvents (such ethanol methol), Tf2O-catalyzed could be realized, while stoichiometric Tf2O was required to promote full transformation with isopropanol tert-butanol). The reaction featured substrate scope, functional group compatibility, diastereoselectivity. This method further applied oxytrifluoromethylselenolation, aminotrifluoromethylselenolation nucleophiles under modified conditions. A mechanism involving seleniranium ion proposed based on the preliminary results.

Язык: Английский

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Selective Ni-catalyzed cross-electrophile coupling of alkynes, fluoroalkyl halides, and vinyl halides

Chinese Chemical Letters, Год журнала: 2021, Номер 33(8), С. 4074 - 4078

Опубликована: Дек. 26, 2021

Язык: Английский

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