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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...

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Autores principales: Cooper, Lisa, Alonso, José Miguel, Eagling, Louise, Newson, Helen, Herath, Sachini, Thomson, Christopher, Lister, Andrew, Howsham, Catherine, Cox, Brian, Muñoz, María Paz
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2018
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.
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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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