Modular Synthesis of Fully‐Substituted and Configuration‐Defined Alkyl Vinyl Ethers Enabled by Dual‐Functional Copper Catalysis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(11)

Опубликована: Янв. 10, 2024

Here we present a modular, chemo-, regio-, and stereoselective synthesis of fully-substituted configuration-defined alkyl vinyl ethers (AVEs) using simple chemical feedstocks. The distinctive approach involves the chemo- regioselective functionalization CF

Язык: Английский

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A Hexavalent Tellurium-Based Chalcogen Bonding Catalysis Platform: High Catalytic Activity and Controlling of Selectivity

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 13, 2025

Herein, we describe a hexavalent tellurium-based chalcogen bonding catalysis platform capable of addressing reactivity and selectivity issues. This research demonstrates that tellurium salts can serve as class highly active catalysts for the first time. The centers in these have only one exposed interaction site, thus providing favorable condition controlling reaction selectivity. advantages were demonstrated by their remarkable catalytic activity cyanidation difluorocyclopropenes through C-F bond activation, which otherwise low reactive under strong Lewis acids or inaccessible representative divalent/tetravalent donors. catalyst was further highlighted its capability to address previously unresolved problem associated with acid approach, upon using some less silyl enol ethers nucleophiles functionalization difluorocyclopropenes. generality this versatile application different systems. differentiate two similar free OH groups glycosyl acceptors achieve excellent regio- stereoselectivity synthesis disaccharides, tetravalent gave Mechanistic investigation suggests catalyst-glycosyl donor-acceptor ternary supramolecular complex is operative.

Язык: Английский

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B(C6F5)3-catalyzed selective C–H chalcogenation of arenes and heteroarenes

Chem, Год журнала: 2024, Номер 10(9), С. 2901 - 2915

Опубликована: Июнь 27, 2024

The synthesis of organochalcogenides remains a valuable area research due to their widespread biological applications, particularly in pharmaceuticals. Herein, our study details the B(C6F5)3-catalyzed Csp2–H functionalization diverse arenes, heteroarenes, and pharmacophores with thiosuccinimides or selenosuccinimides, providing selective access chalcogenated products. This protocol enables late-stage chalcogenation drug molecules such as anti-inflammatory naproxen, estrogen steroid hormone estradiol derivatives, industrially relevant trifluoromethylthiolation reaction. Furthermore, this C–S coupling methodology provides facile metal-free route synthesize vortioxetine, an antidepressant drug, plethora significant organic motifs. Detailed NMR, EPR analyses, density functional theory (DFT) computational studies indicate that elongation thiosuccinimide N–S bond is assisted by boron-centered adduct, which then leads stable ion pair arene. analysis shows transient radical pair, potentially off-cycle species, not directly involved catalytic process.

Язык: Английский

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B(C₆F₅)₃/Chiral Phosphoric Acid Promoted Asymmetric C-3 gem-Difluoroalkylation of Quinoxalin-2-ones with Difluoroenoxysilanes

Organic Letters, Год журнала: 2024, Номер 26(31), С. 6551 - 6555

Опубликована: Июль 30, 2024

The asymmetric Mannich-type reaction of quinoxalin-2-ones with difluoroenoxysilanes has been developed for the synthesis chiral gem-difluoroalkylated quinoxalin-2-ones. worked in presence phosphoric acid CPA 1 and B(C6F5)3 THF at room temperature. exhibited a good substrate scope furnishing products yields (up to 97%) up 96% ee.

Язык: Английский

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Cryogenic Organometallic Carbon–Fluoride Bond Functionalization with Broad Functional Group Tolerance

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Фев. 6, 2025

The unique properties of fluorinated organic compounds have received intense interest and conquered a myriad applications in the chemical pharmaceutical sciences. Today, an impressive range alkyl fluorides are commercially available, there many practical methods to make them exist. However, unmatched stability inertness C–F bond largely limited its synthetic value, which is very different from widely accepted utility chlorides, bromides, iodides that serve everyday as "workhorse" building blocks countless carbon–carbon forming reactions. This study demonstrates high-yielding functionalization under mild conditions, i.e., at temperatures low −78 °C, short reaction times with unconventional chemoselectivity. Cryogenic Csp3–F cleavage using fluorophilic organoaluminum together fast nucleophile transfer intermediate ate complexes forge bonds unactivated primary, secondary, tertiary alike. method, exploits Al–F thermodynamic driving force, highly selective toward functionalization, whereas other functional groups including chloride, bromide, iodide, aryl halide, alkenyl, alkynyl, difluoroalkyl, trifluoromethyl, ether, ester, hydroxyl, acetal, heteroaryl, nitrile, nitro, amide tolerated, unexpected reversal long-standing main group organometallic halide cross-coupling reactivity compatibility patterns. As result, strongest single chemistry can now be selectively targeted arylation, alkylation, alkenylation, alkynylation reactions used late-stage complementary currently available methods.

Язык: Английский

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Catalytic photoinduced deoxygenation via B(C6F5)3-enabled OAT for aromatic C−H amination of alkylarenes

Research Square (Research Square), Год журнала: 2025, Номер unknown

Опубликована: Апрель 7, 2025

The catalytic deoxygenation of N − OH bonds to generate N-centered radicals remains a significant challenge due the high bond dissociation energy and reliance on stoichiometric auxiliaries or activators. Herein, we report B(C₆F₅)₃-catalyzed photoinduced strategy that enables direct aromatic C(sp²) H amination alkylarenes using N-hydroxyphthalimides (NHPIs) as nitrogen sources. Mechanistic studies reveal in situ formation PhthN O−B(C₆F₅)₃ anion intermediate facilitates an unusual transfer (EnT)-mediated O homolysis, generating phthalimidyl radical (PhthN•) while regenerating borane catalyst. This method overrides conventional preference for benzylic C oxidation, achieving exclusive with broad substrate scope, including electron-rich/poor alkylarenes, heteroarenes, biomolecules. protocol operates under mild conditions, avoids organic auxiliaries/activators, produces H₂O sole byproduct, thus, making it promising option supplant existing strategies arene amination. Applications in late-stage functionalization pharmaceuticals synthesis nilotinib precursor highlight its synthetic utility. study establishes B(C₆F₅)₃ versatile oxygen atom (OAT) reagent photochemistry, opening avenues sustainable generation.

Язык: Английский

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Modular Synthesis of Fully‐Substituted and Configuration‐Defined Alkyl Vinyl Ethers Enabled by Dual‐Functional Copper Catalysis

Angewandte Chemie, Год журнала: 2024, Номер 136(11)

Опубликована: Янв. 10, 2024

Abstract Here we present a modular, chemo‐, regio‐, and stereoselective synthesis of fully‐substituted configuration‐defined alkyl vinyl ethers (AVEs) using simple chemical feedstocks. The distinctive approach involves the chemo‐ regioselective functionalization CF 2 unit in gem ‐difluorinated cyclopropanes with O−H C−H nucleophiles specific order. resulting highly functionalized cyclopropanyl then undergo ring‐opening process to produce AVEs. These AVEs are rarely accessible through conventional methods easily transformable. Mechanistic experiments indicate that success this method relies on use dual‐functional copper catalysis, which is involved both subsequent process.

Язык: Английский

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Photocatalytic Decarboxylative Functionalization of Cyclopropenes via Cyclopropenium Cation Intermediates

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(32)

Опубликована: Май 28, 2024

Abstract A photocatalytic decarboxylative functionalization of cyclopropenes is reported. Starting from a broad range redox‐active ester‐substituted cyclopropenes, cyclopropenylphthalimides can be synthesized in the absence nucleophile. Alternatively, different carbon and heteroatom nucleophiles introduced. The transformation proceeds most probably through formation an aromatic cyclopropenium cation, followed by trapping with nucleophiles.

Язык: Английский

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Tris(pentafluorophenyl)borane-Catalyzed Stereoselective C-Glycosylation of Glycals: A Facile Synthesis of Allyl and Alkynyl Glycosides

Synthesis, Год журнала: 2023, Номер 56(06), С. 1026 - 1034

Опубликована: Окт. 5, 2023

Abstract In modern advances, tris(pentafluorophenyl)borane (commonly known as BCF) catalyst has risen to prominence owing its extensive versatility in the use of myriad organic reactions. An efficient and highly stereoselective α-C-glycosylation strategy is presented by employing a catalytic amount B(C6F5)3 under mild reaction conditions en route 2,3-unsaturated C-glycosides. The features broad functional group tolerance including variety glycals coupled with allyltrimethylsilane trimethylsilylphenylacetylene access corresponding allyl- alkynyl-C-glycosides excellent α-selectivity. proceeds good yields via concomitant borane activation glycal donor conditions.

Язык: Английский

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Photocatalytic Decarboxylative Functionalization of Cyclopropenes via Cyclopropenium Cation Intermediates

Angewandte Chemie, Год журнала: 2024, Номер 136(32)

Опубликована: Май 28, 2024

Abstract A photocatalytic decarboxylative functionalization of cyclopropenes is reported. Starting from a broad range redox‐active ester‐substituted cyclopropenes, cyclopropenylphthalimides can be synthesized in the absence nucleophile. Alternatively, different carbon and heteroatom nucleophiles introduced. The transformation proceeds most probably through formation an aromatic cyclopropenium cation, followed by trapping with nucleophiles.

Язык: Английский

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