Air stable, sterically hindered ferrocenyl dialkylphosphines for palladium-catalyzed C-C, C-N, and C-O bond-forming cross-couplings
Air stable, sterically hindered ferrocenyl dialkylphosphines for palladium-catalyzed C-C, C-N, and C-O bond-forming cross-couplings
复制标题
DOI：
10.1021/jo025732j
复制
发表时间：
2002-08-09
影响因子：
3.6
通讯作者：
Hartwig, JF
中科院分区：
文献类型：
--
作者：
Kataoka, N;Shelby, Q;Hartwig, JF
用两步合成法高产率地合成了五苯基二茂铁基二叔丁基膦，并考察了含该配体的配合物催化的各种交叉偶联反应的范围。该配体为芳基卤化物胺化反应和铃木偶联反应提供了一种非常通用的钯催化剂。观察到含有未活化的芳基溴化物或氯化物的胺化反应的周转率约为1000。此外，该配体的络合物在温和的条件下催化了选择性芳基醚的形成。这些反应包括富电子和贫电子的芳基溴化物和氯化物。在含有该配体的催化剂存在下，这些芳基卤化物与无环或环状的仲烷基胺和芳基胺偶联，与伯烷基胺和芳胺偶联，与芳基和伯烷基硼酸偶联。这些最后的偶联反应提供了第一个没有有毒或昂贵的碱的端烷基硼酸与芳基卤化物反应的一般程序。该配体不仅生成了高活性的钯催化剂，而且在溶液和固体中都是空气稳定的。该配体的钯(0)络合物也是空气稳定的固体，只与溶液中的氧反应缓慢。
Pentaphenylferrocenyl di-tert-butylphosphine has been prepared in high yield from a two-step synthetic procedure, and the scope of various cross-coupling processes catalyzed by complexes bearing this ligand has been investigated. This ligand creates a remarkably general palladium catalyst for aryl halide amination and for Suzuki coupling. Turnovers of roughly 1000 were observed for aminations with unactivated aryl bromides or chlorides. In addition, complexes of this ligand catalyzed the formation of selected aryl ethers under mild conditions. The reactions encompassed electron-rich and electron-poor aryl bromides and chlorides. In the presence of catalysts containing this ligand, these aryl halides coupled with acyclic or cyclic secondary alkyl- and arylamines, with primary alkyl- and arylamines, and with aryl- and primary alkylboronic acids. These last couplings provide the first general procedure for reaction of terminal alkylboronic acids with aryl halides without toxic or expensive bases. The ligand not only generates highly active palladium catalysts, but it is air stable in solution and in the solid state. Palladium(0) complexes of this ligand are also air stable as a solid and react only slowly with oxygen in solution.