Synthesis of Spiro[benzo[d][1,3]oxazine-4,4′-isoquinoline]s via [4+1+1] Annulation of N-Aryl Amidines with Diazo Homophthalimides and O₂

Organic Letters, Год журнала: 2022, Номер 24(6), С. 1280 - 1285

Опубликована: Фев. 7, 2022

Synthesis of spiro[benzo[d][1,3]oxazine-4,4'-isoquinoline]s through a unique [4+1+1] annulation N-aryl amidines with diazo homophthalimides and O2 is presented. This unprecedented spirocyclization reaction features readily obtainable substrates, structurally pharmaceutically attractive products, cost-free clean oxygen source, sustainable medium, tolerance broad spectrum functional groups, an interesting mechanism based on sequential C(sp2)-H/C(sp3)-H bond cleavage insertion.

Язык: Английский

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Condition-Controlled Selective Synthesis of Pyranone-Tethered Indazoles or Carbazoles through the Cascade Reactions of N-Nitrosoanilines with Iodonium Ylides

Organic Letters, Год журнала: 2023, Номер 25(24), С. 4422 - 4428

Опубликована: Июнь 8, 2023

Presented herein is a condition-controlled selective synthesis of pyranone-tethered indazoles or carbazole derivatives via the cascade reactions N-nitrosoanilines with iodonium ylides. Mechanistically, formation former involves an unprecedented process including nitroso group-directed C(sp2)–H bond alkylation N-nitrosoaniline ylide followed by intramolecular C-nucleophilic addition to moiety, solvent-assisted cyclohexanedione ring opening, and transesterification/annulation. On contrary, latter initial annulation denitrosation. These developed protocols feature easily controllable selectivity, mild reaction conditions, clean sustainable oxidant (air), valuable products that are structurally diverse. In addition, utility was showcased their facile diverse transformations into synthetically biologically interesting compounds.

Язык: Английский

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Synthesis of 1,7-Fused Indolines Tethered with Spiroindolinone Based on C–H Activation Strategy with Air as a Sustainable Oxidant

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(3), С. 1880 - 1897

Опубликована: Янв. 22, 2024

Herein, we present an efficient synthesis of 1,7-fused indolines tethered with a spiroindolinonyl moiety through the cascade reaction indolin-1-yl(aryl)methanimines diazo oxindoles. To best our knowledge, this is first example in which indoline skeleton was constructed along simultaneous introduction spiro element initiated by C–H bond activation indoline. In forming title product, substrate and coupling partner demonstrated unprecedented pattern latter acts as C1 synthon to participate construction spirocyclic scaffold reductive elimination key seven-membered Ru(II) species using air effective sustainable oxidant regenerate active catalyst. Moreover, studies on cytotoxicity selected products against several human cancer cell lines their potential lead compounds for development anticancer drugs. With notable features such simple economical substrates, pharmaceutically valuable sophisticated skeleton, mild conditions, cost-free oxidants, high efficiency, excellent compatibility diverse functional groups, scalability, method expected find wide applications related areas.

Язык: Английский

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An unusual reaction mode of 1-phenylpyrazolidinones toward diazonaphthalen-2(1H)-ones featuring cascade C(sp²)–H and C(sp³)–H bond cleavage

Organic Chemistry Frontiers, Год журнала: 2021, Номер 8(13), С. 3238 - 3243

Опубликована: Янв. 1, 2021

Herein, a novel synthesis of pyrazolidinone fused 1,3-benzooxazepine derivatives via formal [4 + 3] annulation reaction 1-phenylpyrazolidinones with diazonaphthalen-2(1H)-ones is presented.

Язык: Английский

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Selective Synthesis of 3‐(α‐Fluorovinyl)indoles and 3‐Acylindoles via the Cascade Reactions of 1‐Phenylpyrazolidinones with α,α‐Difluoromethylene Alkynes

Advanced Synthesis & Catalysis, Год журнала: 2021, Номер 363(14), С. 3600 - 3606

Опубликована: Июнь 10, 2021

Abstract Presented herein is a selective synthesis of 3‐(α‐fluorovinyl)indoles and 3‐acylindoles via the coupling 1‐phenylpyrazolidinones with α,α‐difluoromethylene alkynes. Mechanistically, formation resulted from cascade process including Rh(III)‐catalyzed ortho ‐C−H bond cleavage, regioselective triple insertion, pyrazolidinone ring‐opening, indole ring‐formation HF elimination. Interestingly, when this reaction was carried out in CH 3 OH/H 2 O instead CN, situ formed readily undergo hydration to afford 3‐acylindole derivatives. This protocol features controllable selectivity, simultaneous both heterocyclic scaffold monofluoroalkenyl moiety, atom‐economy, substrate diversity, good functional group tolerance redox‐neutral conditions. Anticancer screening selected products against two human cancer cell lines demonstrated their potential as lead compounds for drug development. magnified image

Язык: Английский

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Solvent-Dependent Selective Synthesis of CF₃-Tethered Indazole Derivatives Based on Multiple Bond Activations

Organic Letters, Год журнала: 2023, Номер 25(5), С. 720 - 725

Опубликована: Янв. 27, 2023

Presented herein is a solvent-dependent selective synthesis of CF3-tethered indazole derivatives via the cascade reactions 1-arylpyrazolidinones with trifluoromethyl ynones. Mechanistically, formation title products involves N–H/C–H/C–N/C–C bond cleavage along pyrazole ring and pyrazolidinone opening. For scaffold, 1-phenylpyrazolidinone acts as C2N2 synthon, while ynone serves C1 synthon. Meanwhile, also an enol unit to facilitate opening provide trifluoropropenoxy fragment alkynyl triple migration cleaved moiety. When reaction was run in trifluoroethanol instead DCE, it selectively afforded tethered trifluoroethoxy moiety through situ transesterification. To our knowledge, this first concurrent activation, formation, CF3 migration.

Язык: Английский

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Unsymmetrical relay C–H alkenylation and [2 + 2] cycloaddition ofN-arylsydnones with allenyl acetates leading to quinoline-fused cyclobutanes

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(5), С. 1191 - 1197

Опубликована: Янв. 1, 2023

In this paper, we present a direct, effective and atom-economical access toward quinoline-fused cyclobutane derivatives through Rh( iii )-catalyzed cascade reactions of N -arylsydnones with allenyl acetates.

Язык: Английский

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Synthesis of homophthalimide spironaphthalenones through [5 + 1] spiroannulation of aryl/alkenyl enaminones with diazo homophthalimides

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(17), С. 4282 - 4288

Опубликована: Янв. 1, 2023

Presented herein is a novel synthesis of homophthalimide spironaphthalenones from the cascade reaction enaminones with diazo homophthalimides.

Язык: Английский

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Rh-Catalyzed C–H Activation/Annulation of Enaminones and Cyclic 1,3-Dicarbonyl Compounds: An Access to Isocoumarins

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(9), С. 5348 - 5358

Опубликована: Апрель 3, 2023

A facile access to isocoumarins has been established via rhodium(III)-catalyzed C-H bond activation and intramolecular C-C cascade annulation of enaminones cyclic 1,3-dicarbonyl compounds. The synthetic protocol features a wide range substrates with high functional group tolerance, mild reaction conditions, the selective cleavage enaminone bond. Notably, compounds can in situ-generate iodonium ylide as carbene precursor prepare polycyclic scaffolds by reacting PhI(OAc)2. application this method useful precursors bioactive skeletons is also exemplified.

Язык: Английский

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Synthesis of 3-spirooxindole 3H-indoles through Rh(iii)-catalyzed [4 + 1] redox-neutral spirocyclization of N-aryl amidines with diazo oxindoles

Organic Chemistry Frontiers, Год журнала: 2021, Номер 8(15), С. 4131 - 4137

Опубликована: Янв. 1, 2021

Presented herein is a novel synthesis of 3-spirooxindole 3H-indoles via the coupling and spirocyclization N-aryl amidines with diazo oxindoles.

Язык: Английский

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