Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany.
Chemistry. 2012 Nov 5;18(45):14314-28. doi: 10.1002/chem.201201772. Epub 2012 Sep 27.
(π-Allyl)Ir complexes derived from dibenzocyclooctatetraene and phosphoramidites by cyclometalation are effective catalysts for allylic substitution reactions of linear monosubstituted allylic carbonates. These catalysts provide exceptionally high degrees of regioselectivity and allow the reactions to be run under aerobic conditions. A series of (π-allyl)Ir complexes were prepared and characterized by X-ray crystal structure analyses. An allylic amination with aniline displayed different resting states depending on the presence of a strong base. DFT calculations were carried out on the mechanistic aspects of these reactions. The results suggest that for the (π-allyl)Ir complexes, the formation and reactions with nucleophiles proceed with comparable rates.
通过环金属化作用得到的二苯并环辛四烯和磷酰胺衍生的（π-烯丙基）Ir 配合物是线性单取代烯丙基碳酸酯的烯丙基取代反应的有效催化剂。这些催化剂提供了非常高的区域选择性，并允许在有氧条件下进行反应。通过 X 射线晶体结构分析对一系列（π-烯丙基）Ir 配合物进行了制备和表征。与苯胺的烯丙基胺化显示出不同的休眠状态，具体取决于强碱的存在。对这些反应的机理方面进行了 DFT 计算。结果表明，对于（π-烯丙基）Ir 配合物，其形成和与亲核试剂的反应具有相当的速率。
