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Rh(I)/Rh(III) catalyst-controlled divergent aryl/heteroaryl C–H bond functionalization of picolinamides with alkynes
The ability to establish switchable site-selectivity through catalyst control in the direct functionalization of molecules that contain distinct C–H bonds remains a demanding challenge that would enable the construction of diverse scaffolds from the same starting materials. Herein we describe the re...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Royal Society of Chemistry
2015
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5950197/ https://www.ncbi.nlm.nih.gov/pubmed/29861907 http://dx.doi.org/10.1039/c5sc01885d |
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author | Martínez, Ángel Manu Echavarren, Javier Alonso, Inés Rodríguez, Nuria Gómez Arrayás, Ramón Carretero, Juan C. |
author_facet | Martínez, Ángel Manu Echavarren, Javier Alonso, Inés Rodríguez, Nuria Gómez Arrayás, Ramón Carretero, Juan C. |
author_sort | Martínez, Ángel Manu |
collection | PubMed |
description | The ability to establish switchable site-selectivity through catalyst control in the direct functionalization of molecules that contain distinct C–H bonds remains a demanding challenge that would enable the construction of diverse scaffolds from the same starting materials. Herein we describe the realization of this goal, namely a divergent heteroaryl/aryl C–H functionalization of aromatic picolinamide derivatives, targeting two distinct C–H sites, either at the pyridine ring or at the arene unit, to afford isoquinoline or ortho-olefinated benzylamine (or phenethylamine) derivatives. This complementary reactivity has been achieved on the basis of a Rh(III)/Rh(I) switch in the catalyst, resulting in different mechanistic outcomes. Notably, a series of experimental and DFT mechanistic studies revealed important insights about the mechanism of the reaction and reasons behind the divergent regiochemical outcome. |
format | Online Article Text |
id | pubmed-5950197 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2015 |
publisher | Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-59501972018-06-01 Rh(I)/Rh(III) catalyst-controlled divergent aryl/heteroaryl C–H bond functionalization of picolinamides with alkynes Martínez, Ángel Manu Echavarren, Javier Alonso, Inés Rodríguez, Nuria Gómez Arrayás, Ramón Carretero, Juan C. Chem Sci Chemistry The ability to establish switchable site-selectivity through catalyst control in the direct functionalization of molecules that contain distinct C–H bonds remains a demanding challenge that would enable the construction of diverse scaffolds from the same starting materials. Herein we describe the realization of this goal, namely a divergent heteroaryl/aryl C–H functionalization of aromatic picolinamide derivatives, targeting two distinct C–H sites, either at the pyridine ring or at the arene unit, to afford isoquinoline or ortho-olefinated benzylamine (or phenethylamine) derivatives. This complementary reactivity has been achieved on the basis of a Rh(III)/Rh(I) switch in the catalyst, resulting in different mechanistic outcomes. Notably, a series of experimental and DFT mechanistic studies revealed important insights about the mechanism of the reaction and reasons behind the divergent regiochemical outcome. Royal Society of Chemistry 2015-10-01 2015-06-29 /pmc/articles/PMC5950197/ /pubmed/29861907 http://dx.doi.org/10.1039/c5sc01885d Text en This journal is © The Royal Society of Chemistry 2015 http://creativecommons.org/licenses/by/3.0/ This article is freely available. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (CC BY 3.0) |
spellingShingle | Chemistry Martínez, Ángel Manu Echavarren, Javier Alonso, Inés Rodríguez, Nuria Gómez Arrayás, Ramón Carretero, Juan C. Rh(I)/Rh(III) catalyst-controlled divergent aryl/heteroaryl C–H bond functionalization of picolinamides with alkynes |
title | Rh(I)/Rh(III) catalyst-controlled divergent aryl/heteroaryl C–H bond functionalization of picolinamides with alkynes
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title_full | Rh(I)/Rh(III) catalyst-controlled divergent aryl/heteroaryl C–H bond functionalization of picolinamides with alkynes
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title_fullStr | Rh(I)/Rh(III) catalyst-controlled divergent aryl/heteroaryl C–H bond functionalization of picolinamides with alkynes
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title_full_unstemmed | Rh(I)/Rh(III) catalyst-controlled divergent aryl/heteroaryl C–H bond functionalization of picolinamides with alkynes
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title_short | Rh(I)/Rh(III) catalyst-controlled divergent aryl/heteroaryl C–H bond functionalization of picolinamides with alkynes
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title_sort | rh(i)/rh(iii) catalyst-controlled divergent aryl/heteroaryl c–h bond functionalization of picolinamides with alkynes |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5950197/ https://www.ncbi.nlm.nih.gov/pubmed/29861907 http://dx.doi.org/10.1039/c5sc01885d |
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