Orthogonal Pd- and Cu-based catalyst systems for C- and N-arylation of oxindoles
Orthogonal Pd- and Cu-based catalyst systems for C- and N-arylation of oxindoles
复制标题
DOI：
10.1021/ja803179s
复制
发表时间：
2008-07-23
影响因子：
15
通讯作者：
Buchwald, Stephen L.
中科院分区：
文献类型：
--
作者：
Altman, Ryan A.;Hyde, Alan M.;Buchwald, Stephen L.
在未保护的羟吲哚与卤代芳烃的交叉偶联反应中，钯基和铜基催化剂体系表现出正交的化学选择性。基于Pd-二烷基联芳基膦的催化剂体系在3位化学选择性地芳基化羟吲哚，而使用基于Cu-二胺的催化剂体系，芳基化仅发生在氮上。相关的L1 Pd（Ar）（oxindolate）和二胺-Cu（oxindolate）物种进行计算检查，以获得所观察到的化学选择性的控制功能的机理洞察。
In the cross-coupling reactions of unprotected oxindoles with aryl halides, Pd- and Cu-based catalyst systems displayed orthogonal chemoselectivity. A Pd-dialkylbiarylphosphine-based catalyst system chemoselectively arylated oxindole at the 3 position, while arylation occurred exclusively at the nitrogen using a Cu-diamine-based catalyst system. Computational examination of the relevant L1Pd(Ar)(oxindolate) and diamine-Cu(oxindolate) species was performed to gain mechanistic insight into the controlling features of the observed chemoselectivity.