Abstract

The syntheses of fluorinated cyclopentanone derivatives, which have pharmaceutical and agrochemical importance are reported. The catalytic reaction of copper(I) and nickel(II) difluorocarbenes with silyl dienol ethers afforded 4,4-difluoro- and 5,5-difluorocyclopent-1-en-1-yl silyl ethers, respectively. The fluorine-directed and -activated Nazarov cyclization of 1-fluorovinyl vinyl ketones, which were prepared from silyl dienol ethers and free difluorocarbene, proceeded efficiently to afford 2-fluorocyclopent-2-en-1-ones. Moreover, fluorine-­directed Nazarov cyclizations of 2,2-difluorovinyl vinyl ketones and 1-(trifluoromethyl)vinyl vinyl ketones afforded 3-fluorocyclopent-2-en-1-ones and 5-(trifluoromethyl)cyclopent-2-en-1-ones, respectively. In addition, derivatization of ring-difluorinated products also provided 3-fluorocyclopent-2-en-1-ones.

The syntheses of fluorinated cyclopentanone derivatives, which have pharmaceutical and agrochemical importance are reported. The catalytic reaction of copper(I) and nickel(II) difluorocarbenes with silyl dienol ethers afforded 4,4-difluoro- and 5,5-difluorocyclopent-1-en-1-yl silyl ethers, respectively. The fluorine-directed and -activated Nazarov cyclization of 1-fluorovinyl vinyl ketones, which were prepared from silyl dienol ethers and free difluorocarbene, proceeded efficiently to afford 2-fluorocyclopent-2-en-1-ones. Moreover, fluorine-­directed Nazarov cyclizations of 2,2-difluorovinyl vinyl ketones and 1-(trifluoromethyl)vinyl vinyl ketones afforded 3-fluorocyclopent-2-en-1-ones and 5-(trifluoromethyl)cyclopent-2-en-1-ones, respectively. In addition, derivatization of ring-difluorinated products also provided 3-fluorocyclopent-2-en-1-ones.

中文翻译：

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氟代环戊酮衍生物的区域选择性合成：使用过渡金属-二氟卡宾配合物和游离二氟卡宾的环构建策略

摘要

据报道，具有药用和农用化学重要性的氟化环戊酮衍生物的合成。铜（I）和镍（II）二氟卡宾与甲硅烷基二烯醇醚的催化反应分别得到4,4-二氟-和5,5-二氟环戊-1-烯-1-基甲硅烷基醚。由甲硅烷基二烯醇醚和游离的二氟卡宾制备的1-氟乙烯基乙烯基酮的氟导向和活化的纳扎罗夫环化反应有效地进行，得到了2-氟环戊-2-烯-1-酮。此外，对2,2-二氟乙烯基乙烯基酮和1-（三氟甲基）乙烯基乙烯基酮进行氟导向的纳扎罗夫环化反应，得到了3-氟环戊-2-烯-1-酮和5-（三氟甲基）环戊-2-烯-1-酮一个。另外，环二氟化产物的衍生化也提供了3-氟环戊-2-烯-1-酮。

据报道，具有药用和农用化学重要性的氟化环戊酮衍生物的合成。铜（I）和镍（II）二氟卡宾与甲硅烷基二烯醇醚的催化反应分别得到4,4-二氟-和5,5-二氟环戊-1-烯-1-基甲硅烷基醚。由甲硅烷基二烯醇醚和游离的二氟卡宾制备的1-氟乙烯基乙烯基酮的氟导向和活化的纳扎罗夫环化反应有效地进行，得到了2-氟环戊-2-烯-1-酮。此外，对2,2-二氟乙烯基乙烯基酮和1-（三氟甲基）乙烯基乙烯基酮进行氟导向的纳扎罗夫环化反应，得到了3-氟环戊-2-烯-1-酮和5-（三氟甲基）环戊-2-烯-1-酮一个。另外，环二氟化产物的衍生化也提供了3-氟环戊-2-烯-1-酮。