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Multicomponent Dearomative Difluoroalkylation of Isoquinolines with Difluorinated Silyl Enol Ethers: Divergent Synthesis of <i>gem</i>-Difluorinated Heterocycles

Miaomiao Mu, Saimei Liu, Yuru He, Jǐnjīng Xǔ, Haijian Wu, Qiyuan Du, Manman Sun, Jianguo Yang, Zhiming Wang

2023Organic Letters17 citationsDOI

Abstract

A multicomponent dearomative difluoroalkylation of isoquinolines has been developed with difluorinated silyl enol ethers serving as poor nucleophiles without an additional transition-metal or organic catalyst. The sequential oxidative rearomatization under different alkaline conditions provides a controllable formal C–H difluoroalkylation and difluoromethylation method for isoquinolines without peroxide or metal oxidant. A series of isoquinolines including a pharmaceutical, phenanthridine, quinolines, and difluorinated silyl enol ethers were suitable substrates to construct gem -difluorinated heterocycles. The inexpensive starting materials, mild reaction conditions, and simple operation also show practical and environmentally benign advantages.

Topics & Concepts

ChemistrySilylationEnolCombinatorial chemistryOrganic chemistryMedicinal chemistryCatalysisFluorine in Organic ChemistryCatalytic C–H Functionalization MethodsCyclopropane Reaction Mechanisms
Multicomponent Dearomative Difluoroalkylation of Isoquinolines with Difluorinated Silyl Enol Ethers: Divergent Synthesis of <i>gem</i>-Difluorinated Heterocycles | Litcius