Ni- or Cu-catalyzed cross-coupling reaction of alkyl fluorides with Grignard reagents
Ni- or Cu-catalyzed cross-coupling reaction of alkyl fluorides with Grignard reagents
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DOI：
10.1021/ja034201p
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发表时间：
2003-05-14
影响因子：
15
通讯作者：
Kambe, N
中科院分区：
文献类型：
--
作者：
Terao, J;Ikumi, A;Kambe, N
在1，3-丁二烯存在下，正辛基氟与正丙基溴化镁在氯化镍催化下于室温下发生偶联反应，以中等产率得到十一烷。当使用CuCl 2代替NiCl 2时，这种烷基-烷基交叉偶联进行得更有效。在Ni和Cu催化的反应中，1，3-丁二烯的加入显著提高了伯烷基格氏试剂偶联产物的产率。在无1，3-丁二烯存在下，以CuCl 2为催化剂，氟化烷基与叔烷基和苯基格氏试剂进行了高效的反应，得到了高产率的偶联产物。卤代烷混合物（R−X; X = F，Cl，Br）与nC 5 H11 MgBr的竞争反应表明，卤化物的反应活性按R−Cl < R−F < R−Br的顺序增加。相反，在Cu催化的PhMgBr反应中，反应活性以R-Cl <R-Br <R-F的顺序增加。
n-Octyl fluoride underwent a cross-coupling reaction withn-propylmagnesium bromide in the presence of 1,3-butadiene using NiCl2as a catalyst at room temperature to give undecane in moderate yields. This alkyl−alkyl cross-coupling proceeded more efficiently when CuCl2was employed instead of NiCl2. Addition of 1,3-butadiene dramatically improved the yields of the coupling products from primary alkyl Grignard reagents in both Ni- and Cu-catalyzed reactions. Alkyl fluorides efficiently reacted with tertiary alkyl and phenyl Grignard reagents using CuCl2in the absence of 1,3-butadiene to afford the coupling products in high yields. The competitive reaction of a mixture of alkyl halides (R−X; X = F, Cl, Br) withnC5H11MgBr showed that the reactivities of the halides increase in the order R−Cl < R−F < R−Br. In contrast, in the Cu-catalyzed reaction with PhMgBr, the reactivities increase in the order R−Cl < R−Br < R−F.