Synthesis of 2‐Trifluoromethyl‐4‐aminoquinolines via Heating‐Promoted Multi‐component Reaction of CF₃‐Imidoyl Sulfoxonium Ylides and Amines with Difluorocarbene as a C1 Synthon^†

Chinese Journal of Chemistry, Год журнала: 2023, Номер 41(23), С. 3205 - 3210

Опубликована: Июль 17, 2023

Comprehensive Summary A thermally‐induced multi‐component reaction of CF 3 ‐substituted imidoyl sulfoxonium ylides (TFISYs), amines and (triphenylphosphonio)difluoroacetate (PDFA) has been developed, allowing a facile access to 2‐trifluoromethyl‐4‐aminoquinolines in high yields. The proceeds smoothly with or without the addition sulfur utilizes difluorocarbene as C1 synthon under simply heating conditions. Mechanistic study reveals that in‐situ generated thiocarbonyl fluoride, isothiocyanate gem ‐difluoroalkene might act key intermediates.

Язык: Английский

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Copper-Mediated Oxidative Chloro- and Bromodifluoromethylation of Phenols

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(44), С. 23899 - 23904

Опубликована: Окт. 25, 2023

The first oxidative chloro- and bromodifluoromethylation of phenols with (CH3)3SiCF2X CuX (X = Cl or Br) in the presence Selectfluor under mild reaction conditions was developed. This protocol provided a practical efficient method for synthesis diverse range biologically valuable synthetically challenging bromodifluoromethyl aryl ethers. Preliminary mechanistic studies suggest that this proceeded through difluorocarbene-involved coupling process.

Язык: Английский

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Transition-metal-free C(sp2)–C(sp3) cross-coupling of α-(pseudo)halo aliphatic ketones with boronic acids via a 1,4-metallate shift

Nature Synthesis, Год журнала: 2023, Номер 2(12), С. 1211 - 1221

Опубликована: Авг. 3, 2023

Язык: Английский

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Enantioselective construction of chiral gem-difluorinated C2-quaternary indoline via dual MgSO₄–CPA-catalyzed asymmetric Mannich reactions

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(5), С. 1430 - 1436

Опубликована: Янв. 1, 2024

Herein, the synthesis of 2-(3,3-difluoro-2-phenylindolin-2-yl)-1-phenylethan-1-one scaffolds through asymmetric Mannich reactions between 3,3-difluoro cyclic ketimines and simple ketones is described.

Язык: Английский

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Synthesis of gem-Difluorinated 2,3-Dihydrobenzofurans Using Freon-22 via [4 + 1] Annulation of Difluorocarbene and Antitumor Activity Evaluation

Organic Letters, Год журнала: 2024, Номер 26(6), С. 1212 - 1217

Опубликована: Фев. 1, 2024

As an inexpensive industrial chemical, chlorodifluoromethane (Freon-22), despite its relatively low reactivity, can serve as a practical CF

Язык: Английский

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TBAF-Mediated [3+1] Cycloaddition of Difluorocarbene to Access gem-Difluorinated 1,2-Diazetidine Analogues as Potent Anticancer Agents

Organic Letters, Год журнала: 2023, Номер 25(41), С. 7567 - 7572

Опубликована: Окт. 10, 2023

The facile synthesis of gem-difluorinated 1,2-diazetidines was achieved by metal-free [3+1] annulation between C,N-cyclic azomethine imines with difluorocarbene. A library 30 compounds benefiting from the TBAF-mediated cyclization process could be directly assembled in moderate to good yield under mild conditions. plausible mechanism involving difluorocarbene pathway proposed based on carbene trapping and control experiments. Many exhibited dramatic antiproliferative activity 4T1, A549, HeLa tumor cell lines.

Язык: Английский

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On-the-fly ab initio Hagedorn wave-packet dynamics: Single vibronic level fluorescence spectra of difluorocarbene

Physical review. A/Physical review, A, Год журнала: 2025, Номер 111(1)

Опубликована: Янв. 6, 2025

Hagedorn wave packets have been used to compute single vibronic level (SVL) spectra efficiently in model harmonic potentials. To make the approach practical for realistic polyatomic molecules with anharmonicity, here we combine local wave-packet dynamics on-the-fly ab initio dynamics. We then test this method by computing SVL fluorescence of difluorocarbene, a small, floppy molecule very anharmonic potential energy surface. Our time-dependent obtains emission all initial vibrational levels from semiclassical trajectory without need fit individual functions and calculate Franck-Condon factors transitions. show that, whereas global models are inadequate CF2, computed agree well experimental data, especially low excitations. locked icon Physics Subject Headings (PhySH)Electronic transitionsMolecular spectraVibronic effectsAb molecular dynamicsFluorescence spectroscopyPhase space methodsSchroedinger equationSemiclassical methods

Язык: Английский

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Difluorocarbene-Mediated Trimethylsilylation of Nucleophiles with HCF₂N(TMS)₂ as a Silylation Reagent

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 10, 2025

Described herein is the trimethylsilylation of various nucleophiles using a combination HCF3 and NaHMDS. This facile protocol enables rapid construction alkynylsilanes, silyl enol ethers, etc., under mild conditions. Detailed mechanistic studies indicate that trimethylsilicon intermediate formed in situ can be readily attacked by nucleophiles, with activation base NaHMDS difluorocarbene. work first utilizes structure HMDS as silicon source terminal alkynes.

Язык: Английский

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Modular Synthesis of Monofluorinated 1,2,4-Triazoles/1,3,5-Triazines via Defluorinative Annulations of N-CF₃ Imidoyl Chlorides

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 10, 2025

Ring-fluorinated azaheterocycles have wide applications in agrochemicals, pharmaceuticals, and synthesis, which prompt continuous endeavors to expand such heterocyclic families. However, monofluorinated triazaheterocycles hardly been explored. This work reported a novel modular synthesis of 1,2,4-triazoles 1,3,5-triazines, utilizes N-CF3 imidoyl chlorides as unique polyfluoro synthons their defluorinative annulations with hydrazines/imidazines. Further modifications these fluorinated heterocycles highlight the potential method for accessing functional molecules.

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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