Mizukami Yuki, Song Zhiyi, Takahashi Tamotsu
Catalysis Research Center and Graduate School of Life Science, Hokkaido University , Kita-ku, Sapporo 001-0021, Japan.
Org Lett. 2015 Dec 18;17(24):5942-5. doi: 10.1021/acs.orglett.5b02589. Epub 2015 Dec 2.
The halogen exchange reaction of aliphatic fluorine compounds with organic halides as the halogen source was achieved. Treatment of alkyl fluorides (primary, secondary, or tertiary fluorides) with a catalytic amount of titanocene dihalides, trialkyl aluminum, and polyhalomethanes (chloro or bromo methanes) as the halogen source gave the corresponding alkyl halides in excellent yields under mild conditions. In the case of a fluorine/iodine exchange, no titanocene catalyst is needed. Only C-F bonds are selectively activated under these conditions, whereas alkyl chlorides, bromides, and iodides are tolerant to these reactions.
实现了脂肪族氟化合物与作为卤素源的有机卤化物之间的卤素交换反应。在温和条件下，用催化量的二卤代钛茂、三烷基铝和作为卤素源的多卤代甲烷（氯代或溴代甲烷）处理烷基氟化物（伯、仲或叔氟化物），能以优异的产率得到相应的烷基卤化物。在氟/碘交换的情况下，不需要钛茂催化剂。在这些条件下，只有C-F键被选择性地活化，而烷基氯化物、溴化物和碘化物对这些反应具有耐受性。
