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

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 transi...

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Detalles Bibliográficos
Autores principales: Yoshimura, Takayoshi, Maeda, Satoshi, Taketsugu, Tetsuya, Sawamura, Masaya, Morokuma, Keiji, Mori, Seiji
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2017
Materias:
Chemistry
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5618337/
https://www.ncbi.nlm.nih.gov/pubmed/28970877
http://dx.doi.org/10.1039/c7sc00401j
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author Yoshimura, Takayoshi
Maeda, Satoshi
Taketsugu, Tetsuya
Sawamura, Masaya
Morokuma, Keiji
Mori, Seiji
author_facet Yoshimura, Takayoshi
Maeda, Satoshi
Taketsugu, Tetsuya
Sawamura, Masaya
Morokuma, Keiji
Mori, Seiji
author_sort Yoshimura, Takayoshi
collection PubMed
description 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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spelling pubmed-56183372017-10-02 Exploring the full catalytic cycle of rhodium(i)–BINAP-catalysed isomerisation of allylic amines: a graph theory approach for path optimisation Yoshimura, Takayoshi Maeda, Satoshi Taketsugu, Tetsuya Sawamura, Masaya Morokuma, Keiji Mori, Seiji Chem Sci Chemistry 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. Royal Society of Chemistry 2017-06-01 2017-05-03 /pmc/articles/PMC5618337/ /pubmed/28970877 http://dx.doi.org/10.1039/c7sc00401j Text en This journal is © The Royal Society of Chemistry 2017 https://creativecommons.org/licenses/by/3.0/This is an Open Access article distributed under the terms of the Creative Commons Attribution 3.0 Unported License (http://creativecommons.org/licenses/by/3.0/ (https://creativecommons.org/licenses/by/3.0/) ) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
spellingShingle Chemistry
Yoshimura, Takayoshi
Maeda, Satoshi
Taketsugu, Tetsuya
Sawamura, Masaya
Morokuma, Keiji
Mori, Seiji
Exploring the full catalytic cycle of rhodium(i)–BINAP-catalysed isomerisation of allylic amines: a graph theory approach for path optimisation
title Exploring the full catalytic cycle of rhodium(i)–BINAP-catalysed isomerisation of allylic amines: a graph theory approach for path optimisation
title_full Exploring the full catalytic cycle of rhodium(i)–BINAP-catalysed isomerisation of allylic amines: a graph theory approach for path optimisation
title_fullStr Exploring the full catalytic cycle of rhodium(i)–BINAP-catalysed isomerisation of allylic amines: a graph theory approach for path optimisation
title_full_unstemmed Exploring the full catalytic cycle of rhodium(i)–BINAP-catalysed isomerisation of allylic amines: a graph theory approach for path optimisation
title_short Exploring the full catalytic cycle of rhodium(i)–BINAP-catalysed isomerisation of allylic amines: a graph theory approach for path optimisation
title_sort exploring the full catalytic cycle of rhodium(i)–binap-catalysed isomerisation of allylic amines: a graph theory approach for path optimisation
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5618337/
https://www.ncbi.nlm.nih.gov/pubmed/28970877
http://dx.doi.org/10.1039/c7sc00401j
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