Emerging Trends in Copper-Promoted Radical-Involved C–O Bond Formations

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(32), С. 17527 - 17550

Опубликована: Авг. 2, 2023

The C–O bond is ubiquitous in biologically active molecules, pharmaceutical agents, and functional materials, thereby making it an important group. Consequently, the development of bond-forming reactions using catalytic strategies has become increasingly research topic organic synthesis because more conventional methods involving strong base acid have many limitations. In contrast to ionic-pathway-based methods, copper-promoted radical-mediated formation experiencing a surge interest owing renaissance free-radical chemistry photoredox catalysis. This Perspective highlights appraises state-of-the-art techniques this burgeoning field. contents are organized according different reaction types working models.

Язык: Английский

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Unlocking Diverse π-Bond Enrichment Frameworks by the Synthesis and Conversion of Boronated Phenyldiethynylethylenes

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(14), С. 10167 - 10176

Опубликована: Март 27, 2024

The π-bond enrichment frameworks not only serve as a crucial building block in organic synthesis but also assume pivotal role the fields of materials science, biomedicine, photochemistry, and other related disciplines owing to their distinctive structural characteristics. incorporation various substituents into C═C double bonds tetrasubstituted alkenes is currently highly significant research area. However, with diverse on poses challenge achieving stereoselectivity. Here, we reported an efficient convergent route Cu-catalyzed borylalkynylation both symmetrical unsymmetrical 1,3-diynes, B2pin2, acetylene bromide construction boronated phenyldiethynylethylene (BPDEE) derivatives excellent chemo-, stereo-, regioselectivities. BPDEE could transform novel π-conjugated gem-diphenyldiethynylethylene (DPDEE), vinylphenyldiethynylethylene (VPDEE), phenyltriethynylethylene (PTEE) by stepwise process, which provides flexible platform for complex that were difficult synthesize previous methods. initial optical characterization revealed synthesized molecules exhibited aggregation-induced emission (AIE) properties, further establishes groundwork future applications enriches advances field functional research.

Язык: Английский

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Divergent Construction of Thiochromanes and N-Arylbutanamides via Arylthiodifluoromethyl Radical-Triggered Cascade of Alkenes

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(18), С. 13279 - 13290

Опубликована: Авг. 31, 2023

A strategy utilizing silver-catalyzed oxidative decarboxylation radical cascade cyclization of arylthiodifluoroacetic acids with alkenes for the simple and efficient preparation difluoromethylated thiochromanes 2,2-disubstituted-N-arylbutanamides derivatives has been developed. This approach includes good functional group tolerance, easily accessible starting materials, operational simplicity.

Язык: Английский

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Difluoroalkylation/Lactonization of Alkenes with BrCF₂CO₂K via Photoredox Catalysis: Access to α,α‐Difluoro‐γ‐lactones^†

Chinese Journal of Chemistry, Год журнала: 2023, Номер 41(21), С. 2819 - 2824

Опубликована: Июнь 25, 2023

Comprehensive Summary Due to its unique electronic properties, the difluoromethylene group (CF 2 ) has served as a valuable unity in design of biologically active molecules. Since γ‐lactones display broad range biological α,α‐difluoro‐γ‐lactones may exhibit unexpected activities, and thus their synthesis received increasing attention. Traditional synthetic methods suffer from tedious multi‐ step processes, very few effective have been reported recently. Herein, we describe difunctionalization alkenes with BrCF CO K under photoredox catalysis use boron‐Lewis acid for access α,α‐difluoro‐γ‐lactones. In this transformation, alkene substrates used reagents, including acid, PhB(OH) or BF 3 ·THF, are cheap widely available. High efficiency atom economy make protocol attractive.

Язык: Английский

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Difluorocarbene-Enabled Dehydration of Primary Amides To Access Nitriles

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 16, 2025

A cost-effective and environmentally friendly method for the direct conversion of primary amides to nitriles was developed using commercially available non-toxic ethyl bromodifluoroacetate as a difluorocarbene precursor under metal-free ligand-free conditions. The reaction features high yields tolerates various sensitive moieties, including alkyl, alkenyl, ether, sulfone, sulfoxide, heteroaryl, chloro, bromo, iodo, hydroxyl, nitro, cyano groups, late-stage modification complex molecules is also feasible. Moreover, present effective on large scales, showing potential industrial application.

Язык: Английский

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Photoinduced Iron-Catalyzed Decarboxylation/Isomerization of gem-Difluoroallyl Carboxylic Acid to Access Vinyl Difluoromethylene Units

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 28, 2025

Vinyl difluoromethylene units (−CF−) significantly enhance the bioactivity and physical chemical properties of compounds. Despite recent advances in introducing vinyl units, radical-mediated formation these motifs remains largely unexplored. A novel serial catalytic strategy for selective defluoroalkylation trifluoromethyl alkenes has been developed, utilizing photocatalytic defluorocarboxylation followed by photoinduced iron-catalyzed decarboxylation/isomerization. The reaction involves generating difluoroallyl radicals, tautomerizing to proceeding through radical addition alkylation.

Язык: Английский

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Metal-free phosphine-catalyzed visible-light-induced radical cyclization of alkenes: access to cyclic gem-difluoroacyl scaffolds

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(13), С. 3717 - 3723

Опубликована: Янв. 1, 2024

Visible-light-induced phosphine-catalyzed radical cyclization of bromodifluoroacyl arenes with diverse alkenes, affording a variety cyclic gem -difluoroacyl scaffolds in good to excellent yields.

Язык: Английский

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Base-Dependent Divergent Carbodifluoroalkylation and Halodifluoroalkylation of Alkenes under Visible-Light Irradiation

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(18), С. 13457 - 13471

Опубликована: Сен. 3, 2024

Organic molecules containing a difluoroalkyl group are valuable and versatile chemicals because of their unique physicochemical biological properties. Accordingly, the development efficient practical difluoroalkylation for preparation these compounds is important attractive. Herein, we demonstrate photoredox-catalyzed base-dependent selective carbodifluoroalkylation halodifluoroalkylation alkenes using readily available 2-(allyloxy)arylaldehydes [or 2-(allylamino)arylaldehydes] XCF

Язык: Английский

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Photoinduced Metal-Free Radical Addition/Cyclization of 2-Cyanoaryl Acrylamides to Prepare gem-Difluorinated Naphthyridinone Scaffolds

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(15), С. 10831 - 10843

Опубликована: Июль 11, 2024

Direct construction of

Язык: Английский

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Photo-Induced Difluoromethylation-Cyclization and Domino Amination-Defluorination to 4-(Aminomethyl)-3-fluoro-quinolinones

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Сен. 30, 2024

Herein, we report a visible light-induced difluoromethylation cyclization and subsequent amination-defluorination reaction. This protocol allows efficient to valuable 3-fluoro-quinolinones in moderate excellent yields. A sequential difluoromethylation-cyclization-amination-defluorination mechanism was proposed based on study. Further density functional theory (DFT) calculations revealed that the base K

Язык: Английский

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