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Synthesis of a Novel Type of 2,3′‐BIMs via Platinum‐Catalysed Reaction of Indolylallenes with Indoles
Optimisation, scope and mechanism of the platinum‐catalysed addition of indoles to indolylallenes is reported here to give 2,3′‐BIMs with a novel core structure very relevant for pharmaceutical industry. The reaction is modulated by the electronic properties of the substituents on both indoles, with...
Autores principales: | , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2018
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5947743/ https://www.ncbi.nlm.nih.gov/pubmed/29393548 http://dx.doi.org/10.1002/chem.201705417 |
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author | Cooper, Lisa Alonso, José Miguel Eagling, Louise Newson, Helen Herath, Sachini Thomson, Christopher Lister, Andrew Howsham, Catherine Cox, Brian Muñoz, María Paz |
author_facet | Cooper, Lisa Alonso, José Miguel Eagling, Louise Newson, Helen Herath, Sachini Thomson, Christopher Lister, Andrew Howsham, Catherine Cox, Brian Muñoz, María Paz |
author_sort | Cooper, Lisa |
collection | PubMed |
description | Optimisation, scope and mechanism of the platinum‐catalysed addition of indoles to indolylallenes is reported here to give 2,3′‐BIMs with a novel core structure very relevant for pharmaceutical industry. The reaction is modulated by the electronic properties of the substituents on both indoles, with the 2,3′‐BIMs favoured when electron donating groups are present. Although simple at first, a complex mechanism has been uncovered that explains the different behaviour of these systems with platinum when compared with other metals (e.g. gold). Detailed labelling studies have shown Pt‐catalysed 6‐endo‐trig cyclisation of the indollylallene as the first step of the reaction and the involvement of two cyclic vinyl‐platinum intermediates in equilibrium through a platinum carbene, as the key intermediates of the catalytic cycle towards the second nucleophilic attack and formation of the BIMs. |
format | Online Article Text |
id | pubmed-5947743 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2018 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-59477432018-05-17 Synthesis of a Novel Type of 2,3′‐BIMs via Platinum‐Catalysed Reaction of Indolylallenes with Indoles Cooper, Lisa Alonso, José Miguel Eagling, Louise Newson, Helen Herath, Sachini Thomson, Christopher Lister, Andrew Howsham, Catherine Cox, Brian Muñoz, María Paz Chemistry Full Papers Optimisation, scope and mechanism of the platinum‐catalysed addition of indoles to indolylallenes is reported here to give 2,3′‐BIMs with a novel core structure very relevant for pharmaceutical industry. The reaction is modulated by the electronic properties of the substituents on both indoles, with the 2,3′‐BIMs favoured when electron donating groups are present. Although simple at first, a complex mechanism has been uncovered that explains the different behaviour of these systems with platinum when compared with other metals (e.g. gold). Detailed labelling studies have shown Pt‐catalysed 6‐endo‐trig cyclisation of the indollylallene as the first step of the reaction and the involvement of two cyclic vinyl‐platinum intermediates in equilibrium through a platinum carbene, as the key intermediates of the catalytic cycle towards the second nucleophilic attack and formation of the BIMs. John Wiley and Sons Inc. 2018-03-05 2018-04-20 /pmc/articles/PMC5947743/ /pubmed/29393548 http://dx.doi.org/10.1002/chem.201705417 Text en © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Full Papers Cooper, Lisa Alonso, José Miguel Eagling, Louise Newson, Helen Herath, Sachini Thomson, Christopher Lister, Andrew Howsham, Catherine Cox, Brian Muñoz, María Paz Synthesis of a Novel Type of 2,3′‐BIMs via Platinum‐Catalysed Reaction of Indolylallenes with Indoles |
title | Synthesis of a Novel Type of 2,3′‐BIMs via Platinum‐Catalysed Reaction of Indolylallenes with Indoles |
title_full | Synthesis of a Novel Type of 2,3′‐BIMs via Platinum‐Catalysed Reaction of Indolylallenes with Indoles |
title_fullStr | Synthesis of a Novel Type of 2,3′‐BIMs via Platinum‐Catalysed Reaction of Indolylallenes with Indoles |
title_full_unstemmed | Synthesis of a Novel Type of 2,3′‐BIMs via Platinum‐Catalysed Reaction of Indolylallenes with Indoles |
title_short | Synthesis of a Novel Type of 2,3′‐BIMs via Platinum‐Catalysed Reaction of Indolylallenes with Indoles |
title_sort | synthesis of a novel type of 2,3′‐bims via platinum‐catalysed reaction of indolylallenes with indoles |
topic | Full Papers |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5947743/ https://www.ncbi.nlm.nih.gov/pubmed/29393548 http://dx.doi.org/10.1002/chem.201705417 |
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