Thermocontrolled Radical Nucleophilicity vs Radicophilicity in Regiodivergent C–H Functionalization

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Янв. 8, 2025

The temperature-dependent switching behavior of the saccharin radical is demonstrated, enabling regiodivergent C3–H and C7–H functionalization quinoxalin-2(1H)-ones. was generated through N–Br bond cleavage in N-bromosaccharin (NBSA) observed to transition between radicophile roles. At −10 °C, it utilized as a radicophile, resulting 100% C3-amination, while at +35 acted radical, leading exclusive C7-bromination. Radical nucleophilicity controlled by temperature modulation.

Язык: Английский

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Visible light promoted synthesis of allenes

Catalysis Science & Technology, Год журнала: 2024, Номер 14(18), С. 5143 - 5160

Опубликована: Янв. 1, 2024

This review article summarizes the visible light mediated synthesis of allenes from substrates like 1,3-enynes, propargylic carbonates, homopropargylic alcohols, oxalates, alkynyl diazo compounds, and terminal aziridines.

Язык: Английский

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Copper-Catalyzed Enantioselective Radical Cyanation of Allenic C(sp²)–H Bonds to Access Tri- and Tetrasubstituted Chiral Allenes

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 7741 - 7748

Опубликована: Апрель 25, 2025

Язык: Английский

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Reactions of alkynes with C–S bond formation: recent developments

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(32), С. 6443 - 6484

Опубликована: Янв. 1, 2024

Alkynes are important in organic synthesis. This review mainly focuses on the recent advances (2013–2023) alkynes with C–S bond formation, based more than 30 kinds of sulfur reagents.

Язык: Английский

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Advances in radical peroxidation with hydroperoxides

Beilstein Journal of Organic Chemistry, Год журнала: 2024, Номер 20, С. 2959 - 3006

Опубликована: Ноя. 18, 2024

Organic peroxides have become sought-after functionalities, particularly following the multi-tone consumption in polymer production and success medicinal chemistry. The selective introduction of a peroxide fragment at different positions on target molecule is priority modern reaction design. pioneering Kharasch-Sosnovsky peroxidation became basic universal platform for development methods, with its great potential rapid generation complexity due to ability couple resulting free radicals wide range partners. This review discusses recent advances radical Kharasch-type functionalization organic molecules OOR including free-component couplings. discussion has been structured by type substrate peroxidation: C(sp

Язык: Английский

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Electrochemically Enabled Hydroxyphosphorylation of 1,3-Enynes to Access Phosphinyl-Substituted Propargyl Alcohols

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(15), С. 10796 - 10804

Опубликована: Июль 19, 2024

Catalytic difunctionalization with the direct activation of (O)P-H bonds has been recently established as a potentially robust platform to generate valuable organophosphorus compounds. In terms 1,3-enynes, despite various catalytic methods developed for hydrophosphorylation, radical-mediated hetero-functionalization two different atoms less explored. this study, we disclosed an electrochemically induced hydroxyphosphorylation 1,3-enynes construction phosphinyl-substituted propargyl alcohols. The system involves both arylphosphine oxides and oxygen in ambient air no external metal or additive needed. use electrochemistry ensures regioselective, atom-economic eco-friendly process. This strategy highlights advantages mild reaction conditions, readily available starting materials broad substrate scope, showing its practical synthetic value organic synthesis.

Язык: Английский

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Recent Developments in C‐S, C‐Se Bond Formation via Three‐Component Reactions of Alkynes

European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(46)

Опубликована: Авг. 28, 2024

Abstract Alkynes are valuable building blocks in organic synthesis. They can undergo three‐component difunctionalization to create sulfur or selenium‐containing compounds. Three‐component reactions of alkynes atom economic, practical and regioselective. This review will disscuss decade developments, including C−S C−Se bond formation via thiolation, sulfonylation selenylation. Recent developments be mainly categorized into three types. (1) Radical C−S/S−Se is a hot topic. Reactions initiated by S/Se radicals other exhibit two types selectivities. Photochemical electrochemical under eco‐friendly conditions have been increasingly reported. (2) Some transformations involve electrophilic three‐membered ring intermediates. Thiiraniums, seleniraniums, iodoniums among the most prevalent species. ring‐opening various nucleophiles participate tandem reactions. (3) Metal‐catalyzed reactions, classic category, also discussed text. In following section, we provide an overview based on mechanisms substrates. The roles added reagents discussed.

Язык: Английский

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Copper(II)-Catalyzed Synthesis of Sulfonyl-functionalized Quinone-fused Cyclopenta[b]indoles via Four-component Cascade Annulation

Organic Chemistry Frontiers, Год журнала: 2024, Номер unknown

Опубликована: Окт. 29, 2024

Through crucial selective radical tandem process and intramolecular nucleophilic addition, a facile copper-catalyzed four-component cascade has been realized to selectively construct novel sulfonyl-functionalized quinone-fused cyclopenta[ b ]indole.

Язык: Английский

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Solvent Controlled Chemodivergent Sulfonyl Addition into Enynones: Synthesis of α-Furyl Sulfones and Stereodefined Vinyl Sulfones

The Journal of Organic Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Дек. 28, 2024

Sodium salt of aryl sulfinic acid reacts with enynone in a different manner, yielding α-furyl sulfone and stereodefined vinyl toluene EtOH respectively the presence ZnCl2. The salient features this protocol include chemoselectivity, broad substrate scope, high efficiency, yield, easy purification. synthetic utilities products are demonstrated by cycloaddition cis–trans photoisomerization reactions.

Язык: Английский

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