排序方式: 共有5条查询结果,搜索用时 15 毫秒
1
1.
2.
Dormant versus Evolving Aminopalladated Intermediates: Toward a Unified Mechanistic Scenario in PdII‐Catalyzed Aminations
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Jamshid Rajabi Mélanie M. Lorion Vu Linh Ly Dr. Frédéric Liron Dr. Julie Oble Prof. Dr. Guillaume Prestat Prof. Dr. Giovanni Poli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(6):1539-1546
PdII‐catalyzed alkene aminopalladation and allylic C?H activation are two competing reaction sequences sharing the same reaction conditions. This study aimed at understanding the factors that bias one or the other path in the intramolecular oxidative cyclization of two types of N‐tosyl amidoalkenes. The results obtained are in accord with the initial generation of a high‐energy cyclic (5‐ or 6‐membered) aminopalladated intermediate. However, this latter species can evolve only if the following specific conditions are met: the availability of distocyclic β‐H elimination pathway, the presence of a strong terminal oxidant, or the availability of a carbopalladation pathway. Conversely, the cyclic alkylpalladium complex is only a latent species in equilibrium with the initial substrate and cannot evolve. Such a reactivity hurdle leaves the way open for alternative reactivities such as allylic C?H activation of the olefinic substrate to generate a η3‐allyl complex followed by its interception by the nitrogen nucleophile, [3,3]‐sigmatropic rearrangement, or decomposition. This study proposes a unifying mechanistic picture that connects these competing mechanisms. 相似文献
3.
4.
Back Cover: Dormant versus Evolving Aminopalladated Intermediates: Toward a Unified Mechanistic Scenario in PdII‐Catalyzed Aminations (Chem. Eur. J. 6/2014)
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
5.
1