Issue 6, 2017

Exploring the full catalytic cycle of rhodium(i)–BINAP-catalysed isomerisation of allylic amines: a graph theory approach for path optimisation

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.

Graphical abstract: Exploring the full catalytic cycle of rhodium(i)–BINAP-catalysed isomerisation of allylic amines: a graph theory approach for path optimisation

Supplementary files

Article information

Article type
Edge Article
Submitted
26 Jan 2017
Accepted
02 Apr 2017
First published
03 May 2017
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2017,8, 4475-4488

Exploring the full catalytic cycle of rhodium(I)–BINAP-catalysed isomerisation of allylic amines: a graph theory approach for path optimisation

T. Yoshimura, S. Maeda, T. Taketsugu, M. Sawamura, K. Morokuma and S. Mori, Chem. Sci., 2017, 8, 4475 DOI: 10.1039/C7SC00401J

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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