Application of carbene reactive intermediates in organic synthesis——Ⅲ.Reaction of difluorocarbene wi

来源 :Acta Chimica Sinica(English Edition) | 被引量 : 0次 | 上传用户:sqlwcsqlqs
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The addition of difluorocarbene generated from phenyl(trifluoromethyl)mercury andanhydrous sodium iodide,with trimethylsilyl enol ethers derived from cyclohexanone,cycloheptanone,3-pentanone and acetophenone was described.The corresponding 2,2-difluoro-1-trimethylsilyloxy-cyclopropanes were obtained in good yields.The thermal stability of these cyclopropyl derivativeswas affected by the molecular strain and the nature of their substituents.Thus,1-trimethylsilyloxy-cyclopentene reacted with difluorocarbene to give only 2-fluoro-2-cyclohexen-1-one instead of theexpected 1-trimethylsilyloxy-6,6-difluorobicyclo[3.1.0]hexane,and a mechanism for its formation wasproposed. The addition of difluorocarbene generated from phenyl (trifluoromethyl) mercury and anhydrous sodium iodide, with trimethylsilyl enol ethers derived from cyclohexanone, cycloheptanone, 3-pentanone and acetophenone was. The corresponding 2,2-difluoro-1-trimethylsilyloxy-cyclopropanes were obtained in good yields.The thermal stability of these cyclopropyl derivatives was affected by the molecular strain and the nature of their ... Thus, 1-trimethylsilyloxy-cyclopentene reacted with difluorocarbene to give only 2-fluoro-2-cyclohexen-1-one instead of the expected 1- trimethylsilyloxy-6,6-difluorobicyclo [3.1.0] hexane, and a mechanism for its formation wasproposed.
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