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Chromoselective access to Z- or E- allylated amines and heterocycles by a photocatalytic allylation reaction

The most useful strategies for the alkylation of allylic systems are related to the Tsuji–Trost reaction or the use of different Lewis acids. Herein we report a photocatalytic approach for the allylation reaction of a variety of nucleophiles, such as heteroarenes, amines and alcohols. This method is...

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Autores principales: Martínez-Gualda, Ana María, Cano, Rafael, Marzo, Leyre, Pérez-Ruiz, Raúl, Luis-Barrera, Javier, Mas-Ballesté, Rubén, Fraile, Alberto, de la Peña O’Shea, Víctor A., Alemán, José
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6572830/
https://www.ncbi.nlm.nih.gov/pubmed/31201327
http://dx.doi.org/10.1038/s41467-019-10441-4
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author Martínez-Gualda, Ana María
Cano, Rafael
Marzo, Leyre
Pérez-Ruiz, Raúl
Luis-Barrera, Javier
Mas-Ballesté, Rubén
Fraile, Alberto
de la Peña O’Shea, Víctor A.
Alemán, José
author_facet Martínez-Gualda, Ana María
Cano, Rafael
Marzo, Leyre
Pérez-Ruiz, Raúl
Luis-Barrera, Javier
Mas-Ballesté, Rubén
Fraile, Alberto
de la Peña O’Shea, Víctor A.
Alemán, José
author_sort Martínez-Gualda, Ana María
collection PubMed
description The most useful strategies for the alkylation of allylic systems are related to the Tsuji–Trost reaction or the use of different Lewis acids. Herein we report a photocatalytic approach for the allylation reaction of a variety of nucleophiles, such as heteroarenes, amines and alcohols. This method is compatible with a large variety of pyrroles and indoles, containing different substituents such as electron-withdrawing and electron-donating groups, unprotected nitrogen atoms and bromo derivatives. Moreover, this methodology enables the chromoselective synthesis of Z- or E-allylated compounds. While the use of UV-light irradiation has allowed the synthesis of the previously inaccessible Z-allylated products, E-isomers are prepared simply by changing both the light source to the visible region, and the catalytic system. Based on mechanistic and photochemical proofs, laser flash photolysis studies and DFT calculations, a rational mechanism is presented.
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spelling pubmed-65728302019-06-24 Chromoselective access to Z- or E- allylated amines and heterocycles by a photocatalytic allylation reaction Martínez-Gualda, Ana María Cano, Rafael Marzo, Leyre Pérez-Ruiz, Raúl Luis-Barrera, Javier Mas-Ballesté, Rubén Fraile, Alberto de la Peña O’Shea, Víctor A. Alemán, José Nat Commun Article The most useful strategies for the alkylation of allylic systems are related to the Tsuji–Trost reaction or the use of different Lewis acids. Herein we report a photocatalytic approach for the allylation reaction of a variety of nucleophiles, such as heteroarenes, amines and alcohols. This method is compatible with a large variety of pyrroles and indoles, containing different substituents such as electron-withdrawing and electron-donating groups, unprotected nitrogen atoms and bromo derivatives. Moreover, this methodology enables the chromoselective synthesis of Z- or E-allylated compounds. While the use of UV-light irradiation has allowed the synthesis of the previously inaccessible Z-allylated products, E-isomers are prepared simply by changing both the light source to the visible region, and the catalytic system. Based on mechanistic and photochemical proofs, laser flash photolysis studies and DFT calculations, a rational mechanism is presented. Nature Publishing Group UK 2019-06-14 /pmc/articles/PMC6572830/ /pubmed/31201327 http://dx.doi.org/10.1038/s41467-019-10441-4 Text en © The Author(s) 2019 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.
spellingShingle Article
Martínez-Gualda, Ana María
Cano, Rafael
Marzo, Leyre
Pérez-Ruiz, Raúl
Luis-Barrera, Javier
Mas-Ballesté, Rubén
Fraile, Alberto
de la Peña O’Shea, Víctor A.
Alemán, José
Chromoselective access to Z- or E- allylated amines and heterocycles by a photocatalytic allylation reaction
title Chromoselective access to Z- or E- allylated amines and heterocycles by a photocatalytic allylation reaction
title_full Chromoselective access to Z- or E- allylated amines and heterocycles by a photocatalytic allylation reaction
title_fullStr Chromoselective access to Z- or E- allylated amines and heterocycles by a photocatalytic allylation reaction
title_full_unstemmed Chromoselective access to Z- or E- allylated amines and heterocycles by a photocatalytic allylation reaction
title_short Chromoselective access to Z- or E- allylated amines and heterocycles by a photocatalytic allylation reaction
title_sort chromoselective access to z- or e- allylated amines and heterocycles by a photocatalytic allylation reaction
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6572830/
https://www.ncbi.nlm.nih.gov/pubmed/31201327
http://dx.doi.org/10.1038/s41467-019-10441-4
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