Yoshimura Takayoshi, Maeda Satoshi, Taketsugu Tetsuya, Sawamura Masaya, Morokuma Keiji, Mori Seiji
Institute of Quantum Beam Science , Ibaraki University , Mito 310-8512 , Japan . Email:
Department of Chemistry , Faculty of Science , Hokkaido University , Kita-10, Nishi-8, Kita-ku , Sapporo 060-0810 , Japan . Email:
Chem Sci. 2017 Jun 1;8(6):4475-4488. doi: 10.1039/c7sc00401j. Epub 2017 May 3.
We explored the reaction mechanism of the cationic rhodium(i)-BINAP complex catalysed isomerisation of allylic amines using the artificial force induced reaction method with the global reaction route mapping strategy, which enabled us to search for various reaction paths without assumption of transition states. The entire reaction network was reproduced in the form of a graph, and reasonable paths were selected from the complicated network using Prim's algorithm. As a result, a new dissociative reaction mechanism was proposed. Our comprehensive reaction path search provided rationales for the / and / selectivities of the stereoselective reaction.
我们使用人工力诱导反应方法和全局反应路径映射策略，探索了阳离子铑（I）-联萘酚磷（BINAP）配合物催化的烯丙基胺异构化反应机理，这使我们能够在不假设过渡态的情况下搜索各种反应路径。整个反应网络以图形形式重现，并使用普里姆算法从复杂网络中选择合理路径。结果，提出了一种新的解离反应机理。我们全面的反应路径搜索为立体选择性反应的 / 和 / 选择性提供了理论依据。
