Radical-induced denitration of N-(p-nitrophenyl)propiolamides coupled with dearomatization: access to phosphonylated/trifluoromethylated azaspiro[4.5]-trienones.

A robust dearomative denitration of nitroarene derivatives induced by a radical ipso-cyclization process has been developed, delivering valuable phosphonated or trifluoromethylated azaspiro[4.5]trienones with good functional group tolerance. This represents a convenient and powerful approach to activate nitroarenes in a radical manner.

• Publication year

  2021

• Venue

  Chemical Communications

• Publication date

  2021-12-16

• Fields of study

  Medicine, Chemistry

• Identifiers
  DOI 10.1039/d1cc05724cPMID 34913445
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

• Acyl Radicals from α-Keto Acids: Metal-Free Visible-Light-Promoted Acylation of Heterocycles.

  2021cited by this paper
• Alkylative Dearomatization by Using an Unactivated Aryl Nitro Group as a Leaving Group: Access to Diversified Alkylated Spiro[5.5]trienones.

  2021cited by this paper
• Palladium-Catalyzed Denitrative α-Arylation of Ketones with Nitroarenes.

  2021cited by this paper
• Metal-free spirocyclization of N-arylpropiolamides with glyoxylic acids: access to complex azaspiro-fused tricycles.

  2020cited by this paper
• Electrochemical Oxidative Halogenation of N-Aryl Alkynamides for the Synthesis of Spiro[4.5]trienones.

  2020cited by this paper
• Build-up of double carbohelicenes using nitroarenes: dual role of the nitro functionality as an activating and leaving group†

  2020cited by this paper
• Palladium-catalyzed denitrative Sonogashira-type cross-coupling of nitrobenzenes with terminal alkynes.

  2019cited by this paper
• Phosphinic acids: current status and potential for drug discovery.

  2019cited by this paper
• Copper-Catalyzed Phosphonylation/Trifluoromethylation of N-p-NO2-Benzoylacrylamides Coupled with Dearomatization and Denitration.

  2019cited by this paper
• Visible-light-induced intramolecular charge transfer in the radical spirocyclisation of indole-tethered ynones†

  2019cited by this paper
• Transition-Metal (Cu, Pd, Ni)-Catalyzed Difluoroalkylation via Cross-Coupling with Difluoroalkyl Halides.

  2018cited by this paper
• Dearomative Cascade Photocatalysis: Divergent Synthesis through Catalyst Selective Energy Transfer.

  2018cited by this paper
• Buchwald-Hartwig Amination of Nitroarenes.

  2017cited by this paper
• The Suzuki-Miyaura Coupling of Nitroarenes.

  2017cited by this paper
• Synthesis of 3-alkyl spiro[4,5]trienones by copper-catalyzed oxidative ipso-annulation of activated alkynes with unactivated alkanes.

  2016cited by this paper
• Catalytic asymmetric dearomatization (CADA) reactions of phenol and aniline derivatives.

  2016cited by this paper
• Cerium(IV) ammonium nitrate mediated 5-endo-dig cyclization of α-amino allenylphosphonates to spirodienones.

  2015cited by this paper
• Recent developments in the trifluoromethylation of alkynes.

  2015cited by this paper
• Copper-Catalyzed Thioetherification Reactions of Alkyl Halides, Triphenyltin Chloride, and Arylboronic Acids with Nitroarenes in the Presence of Sulfur Sources.

  2015cited by this paper
• Copper-catalyzed difunctionalization of activated alkynes by radical oxidation-tandem cyclization/dearomatization to synthesize 3-trifluoromethyl spiro[4.5]trienones.

  2015cited by this paper
• Addition of CF3 across unsaturated moieties: a powerful functionalization tool

  2014cited by this paper
• Silver-catalyzed carbon-phosphorus functionalization of N-(p-methoxyaryl)propiolamides coupled with dearomatization: access to phosphorylated aza-decenones.

  2014cited by this paper
• Fluorine in pharmaceutical industry: fluorine-containing drugs introduced to the market in the last decade (2001-2011).

  2014cited by this paper
• Advances in Catalytic Enantioselective Fluorination, Mono-, Di-, and Trifluoromethylation, and Trifluoromethylthiolation Reactions

  2014cited by this paper
• Enantioselective methodologies for the synthesis of spiro compounds.

  2012cited by this paper
• Discorhabdins and pyrroloiminoquinone-related alkaloids.

  2011cited by this paper
• Synthesis and biological evaluation of aryl-phospho-indole as novel HIV-1 non-nucleoside reverse transcriptase inhibitors.

  2011cited by this paper
• Structure, bioactivities, biosynthetic relationships and chemical synthesis of the spirodioxynaphthalenes.

  2010cited by this paper
• Microdose Pharmacokinetics of IDX899 and IDX989, Candidate HIV‐1 Non‐Nucleoside Reverse Transcriptase Inhibitors, Following Oral and Intravenous Administration in Healthy Male Subjects

  2009cited by this paper
• Synthetic methods for azaheterocyclic phosphonates and their biological activity.

  2004cited by this paper
• Denitration of nitroaromatic compounds by arylnitrile radical cations

  2000cited by this paper

• Thermal or Photoinduced Radical Cascade Cyclization to Access CF3/SCF3-Containing Small- and Medium-Membered-Sized N-Heterocycles.

  2025cites this paper
• Access to Methylidene-Azaspiro[4.5]decatrienones via Radical-Promoted Domino Thio-Functionalization/Dearomative Ipso-Annulation.

  2025cites this paper
• Copper-Catalyzed 1,4-Alkylarylation of 1,3-Enynes with Ethers and Aryl Boronic Acids Enabled via C(sp3)-H Functionalization.

  2025cites this paper
• Radical Addition-Induced Dearomative Spirocyclization/1,4-Alkyloximation of Unactivated Arenes.

  2025cites this paper
• Transformative reactions in nitroarene chemistry: C-N bond cleavage, skeletal editing, and N-O bond utilization.

  2025cites this paper
• Selective Synthesis of Mono- and Bis-Phosphorylated (Dihydro)pyrans via TMSCl-Mediated Cascade Phosphorylation Cycloisomerization of Enynones.

  2024cites this paper
• Photo-induced phosphorylation/cyclization of N-homoallyl and N-allyl aldehyde hydrazones to access phosphorylated tetrahydropyridazines and dihydropyrazoles.

  2024cites this paper
• Organocatalyzed Photoelectrochemistry for the Generation of Acyl and Phosphoryl Radicals through Hydrogen Atom-Transfer Process.

  2024cites this paper
• Electrochemical Synthesis of Phosphorylated Indoles and Trp-Containing Oligopeptides.

  2024cites this paper
• Potassium Phosphate-Mediated Synthesis of C4-Phosphorylated Quinolines via Cascade Cycloisomerization of Ynones.

  2024cites this paper
• Visible light-enabled synthesis of phosphorylated indolizine and pyridoindole derivatives via HAT-mediated radical cascade cyclization.

  2023cites this paper
• Visible-light promoted cascade cyanoalkylsulfonylation/ipso-cyclization of N-arylpropiolamides toward sulfonated spiro[4,5]trienones via SO2 insertion.

  2023cites this paper
• CAN-Promoted Thiolative ipso-Annulation of Unactivated N-Benzyl Acrylamides: Access to SCN/SCF3/SO2Ar Containing Azaspirocycles.

  2023cites this paper
• Copper(II)-catalyzed oxidative ipso-annulation of N-arylpropiolamides and biaryl ynones with 1,3-diketones: construction of diketoalkyl spiro-trienones.

  2022cites this paper