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Deproto-metallation of N-arylated pyrroles and indoles using a mixed lithium–zinc base and regioselectivity-computed CH acidity relationship
The synthesis of N-arylated pyrroles and indoles is documented, as well as their functionalization by deprotonative metallation using the base in situ prepared from LiTMP and ZnCl(2)·TMEDA (1/3 equiv). With N-phenylpyrrole and -indole, the reactions were carried out in hexane containing TMEDA which...
Autores principales: | , , , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Beilstein-Institut
2015
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4578368/ https://www.ncbi.nlm.nih.gov/pubmed/26425204 http://dx.doi.org/10.3762/bjoc.11.160 |
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author | Messaoud, Mohamed Yacine Ameur Bentabed-Ababsa, Ghenia Hedidi, Madani Derdour, Aïcha Chevallier, Floris Halauko, Yury S Ivashkevich, Oleg A Matulis, Vadim E Picot, Laurent Thiéry, Valérie Roisnel, Thierry Dorcet, Vincent Mongin, Florence |
author_facet | Messaoud, Mohamed Yacine Ameur Bentabed-Ababsa, Ghenia Hedidi, Madani Derdour, Aïcha Chevallier, Floris Halauko, Yury S Ivashkevich, Oleg A Matulis, Vadim E Picot, Laurent Thiéry, Valérie Roisnel, Thierry Dorcet, Vincent Mongin, Florence |
author_sort | Messaoud, Mohamed Yacine Ameur |
collection | PubMed |
description | The synthesis of N-arylated pyrroles and indoles is documented, as well as their functionalization by deprotonative metallation using the base in situ prepared from LiTMP and ZnCl(2)·TMEDA (1/3 equiv). With N-phenylpyrrole and -indole, the reactions were carried out in hexane containing TMEDA which regioselectively afforded the 2-iodo derivatives after subsequent iodolysis. With pyrroles and indoles bearing N-substituents such as 2-thienyl, 3-pyridyl, 4-methoxyphenyl and 4-bromophenyl, the reactions all took place on the substituent, at the position either adjacent to the heteroatom (S, N) or ortho to the heteroatom-containing substituent (OMe, Br). The CH acidities of the substrates were determined in THF solution using the DFT B3LYP method in order to rationalize the experimental results. |
format | Online Article Text |
id | pubmed-4578368 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2015 |
publisher | Beilstein-Institut |
record_format | MEDLINE/PubMed |
spelling | pubmed-45783682015-09-30 Deproto-metallation of N-arylated pyrroles and indoles using a mixed lithium–zinc base and regioselectivity-computed CH acidity relationship Messaoud, Mohamed Yacine Ameur Bentabed-Ababsa, Ghenia Hedidi, Madani Derdour, Aïcha Chevallier, Floris Halauko, Yury S Ivashkevich, Oleg A Matulis, Vadim E Picot, Laurent Thiéry, Valérie Roisnel, Thierry Dorcet, Vincent Mongin, Florence Beilstein J Org Chem Full Research Paper The synthesis of N-arylated pyrroles and indoles is documented, as well as their functionalization by deprotonative metallation using the base in situ prepared from LiTMP and ZnCl(2)·TMEDA (1/3 equiv). With N-phenylpyrrole and -indole, the reactions were carried out in hexane containing TMEDA which regioselectively afforded the 2-iodo derivatives after subsequent iodolysis. With pyrroles and indoles bearing N-substituents such as 2-thienyl, 3-pyridyl, 4-methoxyphenyl and 4-bromophenyl, the reactions all took place on the substituent, at the position either adjacent to the heteroatom (S, N) or ortho to the heteroatom-containing substituent (OMe, Br). The CH acidities of the substrates were determined in THF solution using the DFT B3LYP method in order to rationalize the experimental results. Beilstein-Institut 2015-08-24 /pmc/articles/PMC4578368/ /pubmed/26425204 http://dx.doi.org/10.3762/bjoc.11.160 Text en Copyright © 2015, Messaoud et al. https://creativecommons.org/licenses/by/2.0https://www.beilstein-journals.org/bjoc/termsThis is an Open Access article under the terms of the Creative Commons Attribution License (https://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (https://www.beilstein-journals.org/bjoc/terms) |
spellingShingle | Full Research Paper Messaoud, Mohamed Yacine Ameur Bentabed-Ababsa, Ghenia Hedidi, Madani Derdour, Aïcha Chevallier, Floris Halauko, Yury S Ivashkevich, Oleg A Matulis, Vadim E Picot, Laurent Thiéry, Valérie Roisnel, Thierry Dorcet, Vincent Mongin, Florence Deproto-metallation of N-arylated pyrroles and indoles using a mixed lithium–zinc base and regioselectivity-computed CH acidity relationship |
title | Deproto-metallation of N-arylated pyrroles and indoles using a mixed lithium–zinc base and regioselectivity-computed CH acidity relationship |
title_full | Deproto-metallation of N-arylated pyrroles and indoles using a mixed lithium–zinc base and regioselectivity-computed CH acidity relationship |
title_fullStr | Deproto-metallation of N-arylated pyrroles and indoles using a mixed lithium–zinc base and regioselectivity-computed CH acidity relationship |
title_full_unstemmed | Deproto-metallation of N-arylated pyrroles and indoles using a mixed lithium–zinc base and regioselectivity-computed CH acidity relationship |
title_short | Deproto-metallation of N-arylated pyrroles and indoles using a mixed lithium–zinc base and regioselectivity-computed CH acidity relationship |
title_sort | deproto-metallation of n-arylated pyrroles and indoles using a mixed lithium–zinc base and regioselectivity-computed ch acidity relationship |
topic | Full Research Paper |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4578368/ https://www.ncbi.nlm.nih.gov/pubmed/26425204 http://dx.doi.org/10.3762/bjoc.11.160 |
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