Exploring the full catalytic cycle of rhodium(i)–BINAP-catalysed isomerisation of allylic amines: a graph theory approach for path optimisation. Issue 6 (3rd May 2017)

• Record Type: Journal Article
• Authors: Yoshimura, Takayoshi; Maeda, Satoshi; Taketsugu, Tetsuya; Sawamura, Masaya; Morokuma, Keiji; Mori, Seiji
• Is Part Of: Chemical science. Volume 8:Issue 6(2017)
• Page Start: 4475
• Page End: 4488
• Publication Date: 2017-05-03
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c7sc00401j
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : The reaction mechanism of the cationic rhodium(i )–BINAP complex catalysed isomerisation of allylic amines was explored using the artificial force induced reaction method with the global reaction route mapping strategy. Abstract : 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.