A versatile difluorovinylation method: Cross-coupling reactions of the 2,2-difluorovinylzinc–TMEDA complex with alkenyl, alkynyl, allyl, and benzyl halides
A versatile difluorovinylation method: Cross-coupling reactions of the 2,2-difluorovinylzinc–TMEDA complex with alkenyl, alkynyl, allyl, and benzyl halides
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DOI：
10.1016/j.jfluchem.2014.12.003
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发表时间：
2015-02
影响因子：
1.9
通讯作者：
T. Ichitsuka;Tsuyoshi Takanohashi;T. Fujita;J. Ichikawa
中科院分区：
文献类型：
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作者：
T. Ichitsuka;Tsuyoshi Takanohashi;T. Fujita;J. Ichikawa
以市售的1，1-二氟乙烯为原料，通过去质子化-转金属反应制备了热稳定的2，2-二氟乙烯基锌-TMEDA络合物。该络合物被成功地应用于过渡金属催化的与多种有机卤化物的交叉偶联反应，从而合成了2，2-二氟乙烯基化合物。二氟乙烯基锌-TMEDA络合物在合适的钯或铜催化剂存在下，烯基、炔基、烯丙基和苯基卤代化合物有效地进行了二氟乙烯基化反应，分别得到了1，1-二氟-1，3-二烯、1，1-二氟-1，4-二烯和(3，3-二氟烯丙基)芳烃。
A thermally stable 2,2-difluorovinylzinc–TMEDA complex was prepared via a deprotonation–transmetallation sequence starting from commercially available 1,1-difluoroethylene. The complex thus formed was successfully applied to transition metal-catalyzed cross-coupling reactions with a wide range of organic halides, which led to the syntheses of 2,2-difluorovinyl compounds. On treatment with the difluorovinylzinc–TMEDA complex in the presence of an appropriate palladium or copper catalyst, alkenyl, alkynyl, allyl, and benzyl halides effectively underwent difluorovinylation to afford 1,1-difluoro-1,3-dienes, 1,1-difluoro-1,3-enynes, 1,1-difluoro-1,4-dienes, and (3,3-difluoroallyl)arenes, respectively.