The Nickel(II)-Catalyzed Direct Benzylation, Allylation, Alkylation, and Methylation of C-H Bonds in Aromatic Amides Containing an 8-Aminoquinoline Moiety as the Directing Group
The Nickel(II)-Catalyzed Direct Benzylation, Allylation, Alkylation, and Methylation of C-H Bonds in Aromatic Amides Containing an 8-Aminoquinoline Moiety as the Directing Group
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DOI：
10.1246/bcsj.20140387
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发表时间：
2015-03-15
影响因子：
4
通讯作者：
Chatani, Naoto
中科院分区：
文献类型：
--
作者：
Aihara, Yoshinori;Wuelbern, Jendrik;Chatani, Naoto
本文报道了以8-氨基喹啉为导向基团的芳香酰胺在镍催化下与卤代烷发生邻位C-H键断裂的直接烷基化反应。各种烷基卤化物，包括苄基、烯丙基、烷基和甲基卤化物（或假卤化物）作为亲电偶联配偶体参与。该反应显示出高的官能团相容性。在间位取代的芳族酰胺的反应中，该反应以高度区域选择性的方式在受阻较少的C-H键处进行，而与取代基的电子性质无关。根据各种机理实验的结果，对C-H烷基化反应的机理进行了讨论。
Direct alkylation via the cleavage of the ortho C-H bonds by a nickel-catalyzed reaction of aromatic amides containing an 8-aminoquinoline moiety as the directing group with alkyl halides is reported. Various alkyl halides, including benzyl, allyl, alkyl, and methyl halides (or pseudo halides) participate as electrophilic coupling partners. The reaction shows a high functional group compatibility. The reaction proceeds in a highly regioselective manner at the less hindered C-H bonds in the reaction of meta-substituted aromatic amides, irrespective of the electronic nature of the substituent. The mechanism responsible for the C-H allcylation reaction is discussed based on the results obtained in a variety of mechanistic experiments.