1,3-二羰基化合物的区域和化学选择性氟化  

Regio-and Chemoselective Fluorination of 1,3-Dicarbonyl Compounds

作　　者：唐林[1] 杨禛 宋维燕 黄依凡 陈思维 TANG Lin;YANG Zhen;SONG Weiyan;HUANG Yifan;CHEN Siwei(College of Chemistry and Chemical Engineering,Xinyang Normal University,Xinyang 464000,China)

机构地区：[1]信阳师范学院化学化工学院

出　　处：《信阳师范学院学报（自然科学版）》2020年第1期106-111,共6页Journal of Xinyang Normal University(Natural Science Edition)

基　　金：国家自然科学基金项目(21602190);河南省科技攻关项目(172102210456);河南省教育厅项目(17A150049);信阳师范学院“南湖学者奖励计划”青年项目;信阳师范学院研究生科研创新基金资助(2018KYJJ43)

摘　　要：以廉价易得的1-氯甲基-4-氟-1,4-重氮化二环[2.2.2]辛烷双(四氟硼酸)盐为氟源,以1,3-二羰基化合物为反应原料在乙醇和水的混合溶剂中可以高效地发生α-位点的区域选择性氟代反应;通过对氟源的用量和反应时间的调控,可以高化学选择性地构建一系列2-单氟代和2,2-双氟代的1,3-二羰基目标化合物.该反应无需过渡金属催化剂、碱性添加剂以及额外的氧化,在室温条件下即可通过单电子氧化还原历程完成,且可进行克规模级别的放大量生产,提供了一种方便而实用的自由基氟化新方法.Highly regioselective α-fluorination of 1,3-dicarbonyl compounds could proceed smoothly by virtue of 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) as the fluorine source in the mixed solvent of ethanol and water. By adjusting the amount of the fluorine source and reaction time, the desired 2-fluoro-and 2,2-difluoro-1,3-dicarbonyl compounds could also be efficiently constructed with an excellent chemoselectivity. The reaction readily took place via a single electron transfer process at room temperature without any transition-metal catalyst,alkaline additive or additional oxidant and could be applicated in gram-scale synthesis, which features a convenient and practical free-radical fluorination.

关 键 词：1 3-二羰基化合物 区域选择性 化学选择性 氟化 自由基 

分 类 号：O622.7[理学—有机化学]