Nickel-Catalyzed Direct Arylation of C(sp3)-H Bonds in Aliphatic Amides via Bidentate-Chelation Assistance
Nickel-Catalyzed Direct Arylation of C(sp3)-H Bonds in Aliphatic Amides via Bidentate-Chelation Assistance
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DOI：
10.1021/ja411715v
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发表时间：
2014-01-22
影响因子：
15
通讯作者：
Chatani, Naoto
中科院分区：
文献类型：
--
作者：
Aihara, Yoshinori;Chatani, Naoto
描述了含有8-氨基喹啉部分的脂肪胺酰胺中C（Sp（3））-H（甲基和甲基）键的直接芳基化，描述了具有芳基卤化物的双齿指导基。氘标记的实验表明C-H键裂解步骤快速且可逆。包括Ni（II）和Ni（0）在内的各种镍复合物都显示出较高的催化活性。一系列机械实验的结果表明，催化反应不是通过Ni（0）/Ni（II）催化循环进行的，而是通过Ni（ii）/Ni（iv）催化循环进行。
The Ni-catalyzed, direct arylation of C(sp(3))-H (methyl and methylene) bonds in aliphatic amides containing an 8-aminoquinoline moiety as a bidentate directing group with aryl halides is described. Deuterium-labeling experiments indicate that the C-H bond cleavage step is fast and reversible. Various nickel complexes including both Ni(II) and Ni(0) show a high catalytic activity. The results of a series of mechanistic experiments indicate that the catalytic reaction does not proceed through a Ni(0)/Ni(II) catalytic cycle, but probably through a Ni(II)/Ni(IV) catalytic cycle.