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Copper‐Catalyzed C(<i>sp</i><sup>3</sup>)− Functionalization and Annulation of 2‐Bromoaryl Oximes with Active Methylene Compounds towards Synthesis of Isoquinoline <i>N</i>‐Oxides

Chandresh K. Patel, Raghuram Gujjarappa, Kamal Kant, Susanta Ghanta, Virender Singh, Arup K. Kabi, Nabil Al‐Zaqri, Chandi C. Malakar

2023Advanced Synthesis & Catalysis20 citationsDOI

Abstract

Abstract The established process proceeds through copper (II)‐catalyzed C( sp 3 )− functionalization of β ‐diketones/ β ‐ketoesters with 2‐bromobenzaldehyde oximes followed by the intramolecular cyclization of in situ generated acylated intermediates to deliver isoquinoline N ‐oxides. The copper(II) acetate catalyzed C−H functionalization showed maximum efficacy at 60 °C in methanol/toluene as solvent. The described reaction conditions were applicable over a wide range of substrates with a variety of functional groups to yield isoquinoline N ‐oxides in yields up to 85%. The developed approach was further elucidated by means of control experiments and DFT calculations.

Topics & Concepts

IsoquinolineChemistryCatalysisMethyleneSurface modificationIntramolecular forceCopperTolueneAnnulationMethanolOrganic chemistryMedicinal chemistryYield (engineering)Physical chemistryMaterials scienceMetallurgyCatalytic C–H Functionalization MethodsSynthesis and Catalytic ReactionsCatalytic Alkyne Reactions
Copper‐Catalyzed C(<i>sp</i><sup>3</sup>)− Functionalization and Annulation of 2‐Bromoaryl Oximes with Active Methylene Compounds towards Synthesis of Isoquinoline <i>N</i>‐Oxides | Litcius