RATIONAL DESIGN IN HOMOGENEOUS CATALYSIS - IR(I)-CATALYZED ADDITION OF ANILINE TO NORBORNYLENE VIA N-H ACTIVATION
RATIONAL DESIGN IN HOMOGENEOUS CATALYSIS - IR(I)-CATALYZED ADDITION OF ANILINE TO NORBORNYLENE VIA N-H ACTIVATION
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DOI：
10.1021/ja00228a022
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发表时间：
1988-09-28
影响因子：
15
通讯作者：
MILSTEIN, D
中科院分区：
文献类型：
--
作者：
CASALNUOVO, AL;CALABRESE, JC;MILSTEIN, D
第一次成功地证明了通过过渡金属催化的NH活化机理的烯烃胺化是以逐步的方式用Ir（I）催化剂和底物苯胺和三亚乙基苯完成的。在这种机制设想的初始NH氧化加成步骤被证明为配合物Ir（PMe3）4PF6，Ir（PMe3）3（C8H14）Cl，和Ir（PEt3）3Cl，所有这些都产生了稳定的顺式苯胺基氢化物配合物与苯胺反应时。第二步，烯烃插入，由Ir（PEt3）2（C2H4）2Cl（1）与苯胺和乙炔的反应完成。所得插入产物Ir（PEt3）2（NHPhC7H10）（H）Cl（6）通过NMR光谱和单晶结构表征。
The first successful demonstration of the amination of an olefin by a transition-metal-catalyzed NH activation mechanism was accomplished in a stepwise manner with an Ir (I) catalyst and the substrates aniline and norbornylene. The initial NH oxidative addition step envisioned in such a mechanism was demonstrated for the complexes Ir (PMe3) 4PF6, Ir (PMe3) 3 (C8H14) Cl, and Ir (PEt3) 3Cl, allof which gave rise to stable cis anilido hydride complexes when reacted with aniline. The second step, olefin insertion, was accomplished from the reaction of Ir (PEt3) 2 (C2H4) 2Cl (1) with aniline and norbornylene. The resulting insertion product, Ir (PEt3) 2 (NHPhC7H10)(H) Cl (6), was characterized by NMR spectroscopy and single-crystal