Arylation of α‐Imino Ketones and their Cyclization with Allenoates: Direct Access to Sterically Hindered Pyrroles

Asian Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 28, 2025

Abstract Herein, we report a calcium‐catalyzed, one‐pot, four‐component reaction to synthesize diversely substituted pyrroles. This atom‐economy involves sequence of reactions that proceed via in situ formation α ‐ imino ketones, Friedel‐Crafts arylation, aza‐cyclization, and aromatization the single pot. The showed broad substrate scope with good yields. We demonstrated gram‐scale synthesis post‐synthetic modifications.

Язык: Английский

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Mechanochemical Cascade Cyclization of Cyclopropyl Ketones with 1,2-Diamino Arenes for the Direct Synthesis of 1,2-Disubstituted Benzimidazoles

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(13), С. 9427 - 9439

Опубликована: Июнь 21, 2024

A mechanochemical synthesis of 1,2-disubstituted benzimidazoles from donor-acceptor cyclopropyl ketones and 1,2-diaminoarenes under metal-free solventless conditions is reported. The reaction does not require inert promoted by a stoichiometric amount 1,1,1,3,3,3-hexafluoroisopropanol. This cascade involves ring-opening, cyclization, retro-Mannich with aryl 1,2-diamines. Compared to its solution-phase counterpart, this approach shows fast reactivity (24 vs 1.5 h). Mechanistic investigations electrospray ionization mass spectrometry helped us propose the mechanism.

Язык: Английский

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Mechanochemical Regioselective [3+3] Annulation of 6‐Amino Uracil with Propargyl Alcohols Catalyzed by a Brønsted Acid/Hexafluoroisopropanol

Chemistry - A European Journal, Год журнала: 2024, Номер 30(48)

Опубликована: Май 10, 2024

A mechanochemistry approach is developed for regioselective synthesis of functionalized dihydropyrido[2,3-d]pyrimidines by milling propargylic alcohols and 6-aminouracils with HFIP/p-TsOH. In the case tert-propargyl alcohols, this [3+3] cascade annulation proceeded through allenylation uracil followed a 6-endo trig cyclization. With sec-propargyl reaction furnished propargylation uracil. This atom economy ball allows access to broad range dihydropyrido[2,3-d]pyrimidine derivatives in excellent yields. We demonstrated gram scale 3 g post-synthetic modifications effect cyclization 5 6.

Язык: Английский

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HFIP-Mediated Cascade Aminomethylation and Intramolecular Cyclization of Allenamides with N,O-Acetals to Access Tetrahydro-β-carboline Derivatives

Chemical Communications, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

A cascade of two C–C bond forming reactions promoted alone by HFIP is described delivering tetrahydro-β-carboline derivatives embedded with an allylic amine functionality.

Язык: Английский

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Diastereoselective Synthesis of Cyclobutanes via Rh-Catalyzed Unprecedented C–C Bond Cleavage of Alkylidenecyclopropanes

Organic Letters, Год журнала: 2025, Номер 27(5), С. 1226 - 1231

Опубликована: Янв. 23, 2025

The stereoselective synthesis of highly substituted cyclobutanes is essential for the development lead candidates in drug discovery. Herein, we present a novel Rh(III)-catalyzed reaction pathway synthesizing cyclobutanes, which involves concerted N-C bond formation and C-C cleavage between 2-aryl quinazolinones alkylidenecyclopropanes. Notably, combination Rh(III) catalyst HFIP solvent plays critical role facilitating cyclobutane rings.

Язык: Английский

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Synthesis of donor-acceptor type 1,1-bis(sulfonyl)cyclopropanes from active bis(sulfonyl)methylene compounds using sulfonium salts

Tetrahedron, Год журнала: 2025, Номер unknown, С. 134514 - 134514

Опубликована: Фев. 1, 2025

Язык: Английский

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HFIP-Promoted Friedel–Crafts Allenylation of Imidazopyridines with Propargyl Alcohols at Room Temperature

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Март 25, 2025

Herein, we report an efficient synthetic protocol for the Friedel–Crafts reaction of imidazo[1,2-a]pyridines with propargyl alcohols in HFIP. Notably, this FC allenylation works without any additional solvent or catalyst and requires neither inert conditions nor heating. In method, HFIP, besides offering hydrogen bonding alcohol, also stabilizes resultant carbocation, thus forming product. This method enables straightforward synthesis 1,3-enynes. The current offers a large substrate diversity good to excellent yields. We demonstrated gram-scale modifications.

Язык: Английский

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Hexafluoroisopropanol (HFIP)-Mediated Intramolecular Cyclization of Allenamides To Access C1-Vinyl Tetrahydro-β-carbolines

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(16), С. 11783 - 11788

Опубликована: Июль 26, 2024

The construction of biologically interesting N-heterocycles under metal-free conditions is a constant goal in industry and academia. Herein, we have developed an hexafluoroisopropanol (HFIP)-mediated intramolecular cyclization allenamides, providing tetrahydro-β-carboline derivatives embedded with C1-vinyl functionality. protocol provided atom-efficiently room temperature broad substrate scope good to excellent yields. potential impact the further highlighted by synthesizing important molecules diversified scaffolds via postsynthetic modifications.

Язык: Английский

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Enantioselective Organocatalyzed One-Pot Synthesis of N-Phenyl Thioether-tethered Tetrasubstituted Dihydropyrrole-3- carbaldehydes

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Herein, we describe an efficient strategy for asymmetric one-pot methodology the synthesis of N -phenyl thioether-tethered tetrasubstituted chiral 4,5-dihydropyrrole-3-carbaldehydes utilizing amine as a organocatalysts.

Язык: Английский

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