Tamamoto Ken, Yamada Shigeyuki, Konno Tsutomu
Faculty of Molecular Chemistry and Engineering, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan.
Beilstein J Org Chem. 2018 Sep 11;14:2375-2383. doi: 10.3762/bjoc.14.213. eCollection 2018.
(1,1,2,2-Tetrafluorobut-3-en-1-yl)zinc bromide was prepared by insertion of the zinc-silver couple into the CF-Br bond of commercially available 4-bromo-3,3,4,4-tetrafluorobut-1-ene in DMF at 0 °C for 0.5 h, The resultant polyfluorinated zinc reagent was found to be thermally stable at ambient temperature and storable for at least 1.5 years in the refrigerator. This CFCF-containing organozinc reagent could be easily transmetallated to copper species, which underwent cross-coupling reactions with various aromatic iodides or acyl chlorides to produce a broad range of CFCF-containing organic molecules in good-to-excellent yields. Therefore, the zinc reagent could become a new and practical synthetic tool for producing functional molecules with a CFCF fragment.
(1,1,2,2 - 四氟丁 - 3 - 烯 - 1 - 基)溴化锌是通过在0℃下于N,N - 二甲基甲酰胺（DMF）中，将锌 - 银偶插入市售的4 - 溴 - 3,3,4,4 - 四氟丁 - 1 - 烯的C - F键中0.5小时制备而成的。发现所得的多氟锌试剂在室温下热稳定，并且在冰箱中可储存至少1.5年。这种含C - F - C - F的有机锌试剂可以很容易地与铜物种进行金属转移反应，后者与各种芳基碘化物或酰氯发生交叉偶联反应，以良好至优异的产率生成各种含C - F - C - F的有机分子。因此，该锌试剂可能成为生产具有C - F - C - F片段的功能分子的一种新型实用合成工具。
