Expeditious Synthesis of Spiroindoline Derivatives via Tandem C(sp²)–H and C(sp³)–H Bond Functionalization of N-Methyl-N-nitrosoanilines

Organic Letters, Journal Year: 2024, Volume and Issue: 26(15), P. 3091 - 3096

Published: April 3, 2024

Presented herein is a novel synthesis of pharmaceutically privileged spiroindoline derivatives via cascade reactions N-methyl-N-nitrosoanilines with diazo homophthalimides. A group mechanistic studies disclosed that the formation product involves an unusual reaction mode N-methyl-N-nitrosoaniline featuring initial C(sp2)–H bond activation/alkylation followed by C(sp3)–H activation/spiroannulation. To our knowledge, this first example in which acts as C3N1 synthon to accomplish formal [4+1] spiroannulation participation N-methyl unit rather than previously reported C2N1 undergo [3+2] annulation without unit. In general, newly developed synthetic protocol features simple and readily accessible starting materials, valuable products, unique mechanism, high efficiency atom-economy, excellent compatibility diverse functional groups, ready scalability.

Language: Английский

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Synthesis of Fused or Spiro Polyheterocyclic Compounds via the Dehydrogenative Annulation Reactions of 2-Arylindazoles with Maleimides

Organic Letters, Journal Year: 2019, Volume and Issue: 21(18), P. 7189 - 7193

Published: Sept. 4, 2019

A dehydrogenative annulation of 2-arylindazoles with maleimides for the switchable synthesis indazolo[2,3-a]pyrrolo[3,4-c]quinolinones or spiroindolo[1,2-b]indazole-11,3′-pyrrolidinones is presented. Mechanistically, formation title compounds involves a Rh(III)-catalyzed C–H metalation 2-arylindazole, followed by maleimide insertion and intramolecular cyclization. Interestingly, selectivity to form fused spiro could be switched resorting different additives. The notable features this protocol include simple substrates excellent atom economy regioselectivity.

Language: Английский

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Ru^II-Catalyzed/NH₂-Assisted Selective Alkenyl C–H [5 + 1] Annulation of Alkenylanilines with Sulfoxonium Ylides to Quinolines

Organic Letters, Journal Year: 2019, Volume and Issue: 21(12), P. 4812 - 4815

Published: June 13, 2019

A novel ruthenium-catalyzed [5 + 1] annulation of 2-alkenylanilines with sulfoxonium ylides was developed for the rapid assembly highly functionalized quinolines. This new catalytic process employs challenging but synthetically ideal free amino functionality to achieve alkenyl C–H activation as one-carbon coupling partners. Various 2-acylquinolines could be obtained good yields and excellent functional group tolerance. Moreover, potential synthetic application this methodology exemplified by several chemical transformations.

Language: Английский

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Asymmetric transformations from sulfoxonium ylides

Chemical Science, Journal Year: 2021, Volume and Issue: 13(5), P. 1192 - 1209

Published: Dec. 8, 2021

Sulfoxonium ylides are important surrogates for diazo compounds, and their use in industry as safer alternatives has been evaluated during recent years. Beyond the known classical transformations, these have also used a surprising plethora of novel intrinsic chemical reactions, especially Bench stability handling an advantage this class organosulfur molecules. Despite this, efficient asymmetric specifically catalytic enantioselective versions, only recently reported, there specific reasons this. This perspective article covers topic from first studies up to latest advances, giving personal perspectives showing main challenges area coming

Language: Английский

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Rhodium-Catalyzed Reaction of Sulfoxonium Ylides and Anthranils toward Indoloindolones via a (4 + 1) Annulation

Organic Letters, Journal Year: 2019, Volume and Issue: 21(17), P. 6653 - 6657

Published: Aug. 19, 2019

A rhodium-catalyzed annulation between aroyl sulfoxonium ylides and anthranils has been developed to synthesize 10H-indolo[1,2-a]indol-10-one derivatives. This reaction started with an unpredented (4 + 1) toward N-(2-formylphenyl) indolones, proceeding the sequential ortho-amination of C–H bond in by insertion N–H carbene. Finally, Aldol condensation constructed second indole ring. procedure features formation two C–N bonds one C═C pot.

Language: Английский

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Application of sulfoxonium ylide in transition-metal-catalyzed C-H bond activation and functionalization reactions

Tetrahedron, Journal Year: 2021, Volume and Issue: 101, P. 132478 - 132478

Published: Oct. 8, 2021

Language: Английский

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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, Journal Year: 2022, Volume and Issue: 24(6), P. 1280 - 1285

Published: Feb. 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.

Language: Английский

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Recent Advances in Metal‐Catalyzed C−H Bond Functionalization Reactions of Sulfoxonium Ylides

Asian Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 11(4)

Published: March 23, 2022

Abstract In recent years, the transition‐metal‐catalyzed functionalization reactions of sulfoxonium ylides have been explored extensively because their usefulness as carbene‐transfer agents, since they can produce metal carbenes through catalysis. Moreover, are safer and advantages simple handling good stability over other counterparts like diazo‐compounds. This review article attempts to highlight advances in metal‐catalyzed C−H ylides.

Language: 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, Journal Year: 2023, Volume and Issue: 25(24), P. 4422 - 4428

Published: June 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.

Language: Английский

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

Organic Letters, Journal Year: 2023, Volume and Issue: 25(5), P. 720 - 725

Published: Jan. 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.

Language: Английский

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