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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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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Rhodium-Catalyzed N-Arylation of 2-Pyridones Enabled by 1,6-Acyl Migratory Rearrangement of 2-Oxypyridines

Organic Letters, Journal Year: 2023, Volume and Issue: 25(11), P. 1974 - 1977

Published: March 15, 2023

An efficient rhodium-catalyzed dearomative rearrangement of 2-oxypyridines with quinone diazides has been developed for the direct synthesis N-arylated pyridones, in which a novel 1,6-O-to-O rather than 1,4-O-to-C acyl achieved under mild reaction conditions.

Language: Английский

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Synthesis of Naphtho[1′,2′:4,5]furo[3,2-b]pyridinones via Ir(III)-Catalyzed C6/C5 Dual C–H Functionalization of N-Pyridyl-2-pyridones with Diazonaphthalen-2(1H)-ones

Organic Letters, Journal Year: 2024, Volume and Issue: 26(4), P. 786 - 791

Published: Jan. 22, 2024

Presented herein is an unprecedented synthesis of naphtho[1′,2′:4,5]furo[3,2-b]pyridinones via Ir(III)-catalyzed C6/C5 dual C–H functionalization N-pyridyl-2-pyridones with diazonaphthalen-2(1H)-ones. This protocol forms C–C and C–O bonds in one pot which diazonaphthalen-2(1H)-ones serve as bifunctional reagents, providing both alkyl aryloxy sources. To the best our knowledge, this first example title compounds by using substrates. Notably, method features operational simplicity, good functional group tolerance, high efficiency, atom economy.

Language: Английский

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Synthesis of CF₃-Substituted N-Heterocyclic Compounds Based on C–H Activation-Initiated Formal [2 + 3] Annulation Featuring with a Latent Nucleophilic Site

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(11), P. 7828 - 7842

Published: May 22, 2024

Presented herein is a novel synthesis of CF

Language: Английский

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Rh(iii)-catalyzed simultaneous [3 + 3]/[5 + 1] annulation of 1-arylpyrazolidinones withgem-difluorocyclopropenes leading to fluorinated pyridopyrimidinone derivatives

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(21), P. 5976 - 5982

Published: Jan. 1, 2022

Presented herein is an efficient and concise synthesis of fluorinated pyridopyrimidinone derivatives through formal [3 + 3]/[5 1] annulation 1-arylpyrazolidinones with gem -difluorocyclopropenes.

Language: Английский

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Selective Synthesis of Pyrazolonyl Spirodihydroquinolines or Pyrazolonyl Spiroindolines under Aerobic or Anaerobic Conditions

Organic Letters, Journal Year: 2022, Volume and Issue: 24(51), P. 9473 - 9478

Published: Dec. 16, 2022

Presented herein is a condition-controlled selective synthesis of pyrazolonyl spirodihydroquinolines or spiroindolines through formal [5 + 1] [4 spiroannulation 2-alkenylanilines with diazopyrazolones. Mechanistically, the formation title products involves initial generation spiro-fused seven-membered ruthenacycle species serving as key intermediate Ru(II)-catalyzed C-H/N-H bonds metalation, carbene formation, and its migratory insertion. When reaction carried out under air, undergoes reductive elimination to afford spirodihydroquinoline. run argon, protonation intramolecular nucleophilic addition furnish spiroindoline. This work provides an atom-economical protocol for effective functionalization alkenyl C(sp2)-H bond, allowing rapid assembly valuable spiroscaffolds broad range substrates.

Language: Английский

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Divergent synthesis of pyrrolizine derivatives through C−H bond functionalization of pyrroles

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(51), P. 6536 - 6539

Published: Jan. 1, 2024

Presented herein is the synthesis of diversely functionalized pyrrolizines from reaction

Language: Английский

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Synthesis of Indenone-Fused Pyran Derivatives from Aryl Enaminones and Cyclopropenones through Unsymmetrical Relay C–H Bond Activation and Double C–C/C–O Bond Formation

Organic Letters, Journal Year: 2024, Volume and Issue: 26(31), P. 6602 - 6607

Published: July 30, 2024

Presented herein is a novel synthesis of indenone-fused pyran derivatives via the cascade reactions aryl enaminones with cyclopropenones. The formation products involves one-pot procedure consisting C–H bond and enamine functionalization along C–C cleavage cyclopropenone 1,3-rearrangement in situ-formed allylic alcohol moiety followed by intramolecular O-nucleophilic addition Me2NH elimination. To our knowledge, this first simultaneous both indenone scaffolds through concurrent unsymmetrical relay activation double C–C/C–O formation. Moreover, usefulness method further showcased its suitability for large-scale synthetic scenarios diverse transformations products.

Language: Английский

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Cu(II)-NHC Catalyzed Insertion of Quinoid Carbenes into cis-Epoxides: Stereoselective Synthesis of trans-Dihydronaphthodioxine

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 28, 2025

A straightforward synthesis of trans-dihydronaphthodioxine has been efficiently accomplished through Cu(II)-NHC catalysis, involving the stereoselective ring opening cis-epoxides with quinoid-carbene. Intramolecular SN2-like substitution facilitates inversion stereochemistry during cis-epoxide opening. This reaction developed under simple conditions, demonstrating a broad substrate scope wide chemoselective profile. Additionally, late-stage functionalization complex bioactive molecules successfully achieved.

Language: Английский

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