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Novel Arylindigoids by Late‐Stage Derivatization of Biocatalytically Synthesized Dibromoindigo
Indigoids represent natural product‐based compounds applicable as organic semiconductors and photoresponsive materials. Yet modified indigo derivatives are difficult to access by chemical synthesis. A biocatalytic approach applying several consecutive selective C−H functionalizations was developed t...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8048522/ https://www.ncbi.nlm.nih.gov/pubmed/33496351 http://dx.doi.org/10.1002/chem.202005191 |
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author | Schnepel, Christian Dodero, Veronica I. Sewald, Norbert |
author_facet | Schnepel, Christian Dodero, Veronica I. Sewald, Norbert |
author_sort | Schnepel, Christian |
collection | PubMed |
description | Indigoids represent natural product‐based compounds applicable as organic semiconductors and photoresponsive materials. Yet modified indigo derivatives are difficult to access by chemical synthesis. A biocatalytic approach applying several consecutive selective C−H functionalizations was developed that selectively provides access to various indigoids: Enzymatic halogenation of l‐tryptophan followed by indole generation with tryptophanase yields 5‐, 6‐ and 7‐bromoindoles. Subsequent hydroxylation using a flavin monooxygenase furnishes dibromoindigo that is derivatized by acylation. This four‐step one‐pot cascade gives dibromoindigo in good isolated yields. Moreover, the halogen substituent allows for late‐stage diversification by cross‐coupling directly performed in the crude mixture, thus enabling synthesis of a small set of 6,6’‐diarylindigo derivatives. This chemoenzymatic approach provides a modular platform towards novel indigoids with attractive spectral properties. |
format | Online Article Text |
id | pubmed-8048522 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-80485222021-04-16 Novel Arylindigoids by Late‐Stage Derivatization of Biocatalytically Synthesized Dibromoindigo Schnepel, Christian Dodero, Veronica I. Sewald, Norbert Chemistry Communications Indigoids represent natural product‐based compounds applicable as organic semiconductors and photoresponsive materials. Yet modified indigo derivatives are difficult to access by chemical synthesis. A biocatalytic approach applying several consecutive selective C−H functionalizations was developed that selectively provides access to various indigoids: Enzymatic halogenation of l‐tryptophan followed by indole generation with tryptophanase yields 5‐, 6‐ and 7‐bromoindoles. Subsequent hydroxylation using a flavin monooxygenase furnishes dibromoindigo that is derivatized by acylation. This four‐step one‐pot cascade gives dibromoindigo in good isolated yields. Moreover, the halogen substituent allows for late‐stage diversification by cross‐coupling directly performed in the crude mixture, thus enabling synthesis of a small set of 6,6’‐diarylindigo derivatives. This chemoenzymatic approach provides a modular platform towards novel indigoids with attractive spectral properties. John Wiley and Sons Inc. 2021-02-26 2021-03-22 /pmc/articles/PMC8048522/ /pubmed/33496351 http://dx.doi.org/10.1002/chem.202005191 Text en © 2021 The Authors. Published by Wiley-VCH GmbH https://creativecommons.org/licenses/by-nc-nd/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ (https://creativecommons.org/licenses/by-nc-nd/4.0/) License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made. |
spellingShingle | Communications Schnepel, Christian Dodero, Veronica I. Sewald, Norbert Novel Arylindigoids by Late‐Stage Derivatization of Biocatalytically Synthesized Dibromoindigo |
title | Novel Arylindigoids by Late‐Stage Derivatization of Biocatalytically Synthesized Dibromoindigo |
title_full | Novel Arylindigoids by Late‐Stage Derivatization of Biocatalytically Synthesized Dibromoindigo |
title_fullStr | Novel Arylindigoids by Late‐Stage Derivatization of Biocatalytically Synthesized Dibromoindigo |
title_full_unstemmed | Novel Arylindigoids by Late‐Stage Derivatization of Biocatalytically Synthesized Dibromoindigo |
title_short | Novel Arylindigoids by Late‐Stage Derivatization of Biocatalytically Synthesized Dibromoindigo |
title_sort | novel arylindigoids by late‐stage derivatization of biocatalytically synthesized dibromoindigo |
topic | Communications |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8048522/ https://www.ncbi.nlm.nih.gov/pubmed/33496351 http://dx.doi.org/10.1002/chem.202005191 |
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