光促二氟烯丙基化合物的E→Z异构化反应  

Visible light promoted E→Z isomerization of difluoroallyl compounds

作　　者：李智 杨春晖 赵红艳 姚朋杰 和振秀 陈景超[1,2] 樊保敏[1,2] Zhi Li;Chunhui Yang;Hongyan Zhao;Pengjie Yao;Zhenxiu He;Jingchao Chen;Baomin Fan(Key Laboratory of Chemistry in Ethnic Medicinal Resources,State Ethnic Affairs Commission&Ministry of Education,Yunnan Minzu University,Kunming650504,China;Yunnan Key Laboratory of Chiral Functional Substance Research and Application,Yunnan Minzu University,Kunming 650504,China)

机构地区：[1]云南民族大学,民族药资源化学国家民族事务委员会-教育部重点实验室,昆明650504 [2]云南民族大学,云南省手性功能物质研究与利用重点实验室,昆明650504

出　　处：《科学通报》2024年第32期4763-4772,共10页Chinese Science Bulletin

基　　金：国家自然科学基金(22361052,22061048,22361053);云南省科技厅项目(202402AN360010,202401BC070018)资助。

摘　　要：有机氟化物在材料、医药以及能源等领域,有着广泛的应用前景.其中,二氟甲基(CF2)作为羰基或醚键的生物电子等排体,其引入能显著改变目标分子的生物活性。目前发展的二氟烯丙基化合物都以得到热力学稳定的反式(E)构型为主.本文建立了由易得的E-二氟烯丙基化合物异构为Z-二氟烯丙基化合物的方法.该反应由2,4,5,6-四咔唑基-1,3-苯二腈(4CzIPN)催化的光化学反应实现,反应温和、操作简便、经济性好,为Z-二氟烯丙基化合物的大量制备建立了高效方法。论文还通过克级反应和产物衍生化对当前反应的实用性进行了研究。机理研究认为,该反应经过三线态-三线态能量转移(TTET)过程完成。Due to the unique properties of fluorine atoms,fluorinated organic compounds play significant roles in pharmaceuticals,pesticides,materiais,fine chemicals,and other fields.About 25%of pharmaceuticals and 30%of pesticide molecules contain at least one fluorine atom.The fluorine atom has high electronegativity and a small atomic radius and is considered a bioisostere of the hydroxyl functional group in medicinal chemistry.Moreover,introducing fluorine atoms can significantly change lead compound's solubility,hydrophobicity,metabolic stability,and bioavailability.Introducing a difluoroallyl group is essential for drug molecules,and the difluoroallyl compounds can be used as important intermediates in synthesizing other fluorinated compounds.Therefore,the synthesis method of difluoroallyl compounds has attracted extensive attention from the synthetic community.The radical coupling reaction of reactive olefins with halogenated difluoroalkanes was developed to synthesize difluoroallyl compounds.However,the current synthesis methods always afforded(E)-allyl difluoride as a main product.

关 键 词：光催化 异构化 二氟烯丙基 4CzIPN 

分 类 号：O621.251[理学—有机化学]