Exploring the full catalytic cycle of rhodium(i)–BINAP-catalysed isomerisation of allylic amines: a graph theory approach for path optimisation† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc00401j Click here for additional data file.

نویسندگان

  • Takayoshi Yoshimura
  • Satoshi Maeda
  • Tetsuya Taketsugu
  • Masaya Sawamura
  • Keiji Morokuma
  • Seiji Mori
چکیده

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 E/Z and S/R selectivities of the stereoselective reaction.

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عنوان ژورنال:

دوره 8  شماره 

صفحات  -

تاریخ انتشار 2017