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 ZnCl2·TMEDA (1/3 equiv). With N-phenylpyrrole and -indole, the reactions were carried out in hexane containing TMEDA which re...
| Main Authors: | , , , , , , , , , , , , |
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| Format: | Article |
| Language: | English |
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Beilstein-Institut
2015-08-01
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| Series: | Beilstein Journal of Organic Chemistry |
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| Online Access: | https://doi.org/10.3762/bjoc.11.160 |
| _version_ | 1818360746455597056 |
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| author | Mohamed Yacine Ameur Messaoud Ghenia Bentabed-Ababsa Madani Hedidi Aïcha Derdour Floris Chevallier Yury S. Halauko Oleg A. Ivashkevich Vadim E. Matulis Laurent Picot Valérie Thiéry Thierry Roisnel Vincent Dorcet Florence Mongin |
| author_facet | Mohamed Yacine Ameur Messaoud Ghenia Bentabed-Ababsa Madani Hedidi Aïcha Derdour Floris Chevallier Yury S. Halauko Oleg A. Ivashkevich Vadim E. Matulis Laurent Picot Valérie Thiéry Thierry Roisnel Vincent Dorcet Florence Mongin |
| author_sort | Mohamed Yacine Ameur Messaoud |
| collection | DOAJ |
| 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 ZnCl2·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. |
| first_indexed | 2024-12-13T21:05:41Z |
| format | Article |
| id | doaj.art-6ebb664c52614cfba9f91d9d557ac8de |
| institution | Directory Open Access Journal |
| issn | 1860-5397 |
| language | English |
| last_indexed | 2024-12-13T21:05:41Z |
| publishDate | 2015-08-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Organic Chemistry |
| spelling | doaj.art-6ebb664c52614cfba9f91d9d557ac8de2022-12-21T23:31:29ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972015-08-011111475148510.3762/bjoc.11.1601860-5397-11-160Deproto-metallation of N-arylated pyrroles and indoles using a mixed lithium–zinc base and regioselectivity-computed CH acidity relationshipMohamed Yacine Ameur Messaoud0Ghenia Bentabed-Ababsa1Madani Hedidi2Aïcha Derdour3Floris Chevallier4Yury S. Halauko5Oleg A. Ivashkevich6Vadim E. Matulis7Laurent Picot8Valérie Thiéry9Thierry Roisnel10Vincent Dorcet11Florence Mongin12Equipe Chimie et Photonique Moléculaires, Institut des Sciences Chimiques de Rennes, UMR 6226, CNRS-Université de Rennes 1, Bâtiment 10A, Case 1003, Campus de Beaulieu, 35042 Rennes, FranceLaboratoire de Synthèse Organique Appliquée, Faculté des Sciences, Université d’Oran 1 Ahmed Ben Bella, BP 1524 El M’Naouer, 31000 Oran, AlgeriaEquipe Chimie et Photonique Moléculaires, Institut des Sciences Chimiques de Rennes, UMR 6226, CNRS-Université de Rennes 1, Bâtiment 10A, Case 1003, Campus de Beaulieu, 35042 Rennes, FranceLaboratoire de Synthèse Organique Appliquée, Faculté des Sciences, Université d’Oran 1 Ahmed Ben Bella, BP 1524 El M’Naouer, 31000 Oran, AlgeriaEquipe Chimie et Photonique Moléculaires, Institut des Sciences Chimiques de Rennes, UMR 6226, CNRS-Université de Rennes 1, Bâtiment 10A, Case 1003, Campus de Beaulieu, 35042 Rennes, FranceUNESCO Chair of Belarusian State University, 14 Leningradskaya Str., Minsk, 220030, BelarusUNESCO Chair of Belarusian State University, 14 Leningradskaya Str., Minsk, 220030, BelarusResearch Institute for Physico-Chemical Problems of Belarusian State University, 14 Leningradskaya Str., Minsk, 220030, BelarusLaboratoire Littoral Environnement et Sociétés, UMRi CNRS 7266, Université de La Rochelle, 17042 La Rochelle, France,Laboratoire Littoral Environnement et Sociétés, UMRi CNRS 7266, Université de La Rochelle, 17042 La Rochelle, France,Centre de Diffractométrie X, Institut des Sciences Chimiques de Rennes, UMR 6226, CNRS-Université de Rennes 1, Bâtiment 10B, Campus de Beaulieu, 35042 Rennes, FranceCentre de Diffractométrie X, Institut des Sciences Chimiques de Rennes, UMR 6226, CNRS-Université de Rennes 1, Bâtiment 10B, Campus de Beaulieu, 35042 Rennes, FranceEquipe Chimie et Photonique Moléculaires, Institut des Sciences Chimiques de Rennes, UMR 6226, CNRS-Université de Rennes 1, Bâtiment 10A, Case 1003, Campus de Beaulieu, 35042 Rennes, FranceThe 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 ZnCl2·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.https://doi.org/10.3762/bjoc.11.160CH acidityindolesiodolysismixed lithium–zinc basespyrroles |
| spellingShingle | Mohamed Yacine Ameur Messaoud Ghenia Bentabed-Ababsa Madani Hedidi Aïcha Derdour Floris Chevallier Yury S. Halauko Oleg A. Ivashkevich Vadim E. Matulis Laurent Picot Valérie Thiéry Thierry Roisnel Vincent Dorcet Florence Mongin Deproto-metallation of N-arylated pyrroles and indoles using a mixed lithium–zinc base and regioselectivity-computed CH acidity relationship Beilstein Journal of Organic Chemistry CH acidity indoles iodolysis mixed lithium–zinc bases pyrroles |
| 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 | CH acidity indoles iodolysis mixed lithium–zinc bases pyrroles |
| url | https://doi.org/10.3762/bjoc.11.160 |
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