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In situ generation of N-unsubstituted imines from alkyl azides and their applications for imine transfer via copper catalysis
Although azides have been widely used in nitrene transfer reactions, in situ generation of N-H imines from azides for downstream transformations has rarely been explored. We report copper-mediated formation of N-unsubstituted aliphatic imines from easily available aliphatic azides using a customized...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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American Association for the Advancement of Science
2017
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5550227/ https://www.ncbi.nlm.nih.gov/pubmed/28808683 http://dx.doi.org/10.1126/sciadv.1700826 |
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author | Hu, Lu Liu, Yahu A. Liao, Xuebin |
author_facet | Hu, Lu Liu, Yahu A. Liao, Xuebin |
author_sort | Hu, Lu |
collection | PubMed |
description | Although azides have been widely used in nitrene transfer reactions, in situ generation of N-H imines from azides for downstream transformations has rarely been explored. We report copper-mediated formation of N-unsubstituted aliphatic imines from easily available aliphatic azides using a customized phenanthroline-based ligand (L(1)*). Through trapping in situ–generated N-H imines, multisubstituted pyridines or indoles were readily synthesized. (13)C-labeled azide was used as part of an isotope labeling study, which suggests that the construction of pyridine derivatives involves a three-component dehydrogenative condensation. The construction of 2,3,5-triaryl pyridines using this method provided evidence supporting a proposed pathway involving both imine formation and abnormal Chichibabin pyridine synthesis. The generation of N-unsubstituted imine intermediates was also confirmed by formation of indole derivatives from alkyl azides. |
format | Online Article Text |
id | pubmed-5550227 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2017 |
publisher | American Association for the Advancement of Science |
record_format | MEDLINE/PubMed |
spelling | pubmed-55502272017-08-14 In situ generation of N-unsubstituted imines from alkyl azides and their applications for imine transfer via copper catalysis Hu, Lu Liu, Yahu A. Liao, Xuebin Sci Adv Research Articles Although azides have been widely used in nitrene transfer reactions, in situ generation of N-H imines from azides for downstream transformations has rarely been explored. We report copper-mediated formation of N-unsubstituted aliphatic imines from easily available aliphatic azides using a customized phenanthroline-based ligand (L(1)*). Through trapping in situ–generated N-H imines, multisubstituted pyridines or indoles were readily synthesized. (13)C-labeled azide was used as part of an isotope labeling study, which suggests that the construction of pyridine derivatives involves a three-component dehydrogenative condensation. The construction of 2,3,5-triaryl pyridines using this method provided evidence supporting a proposed pathway involving both imine formation and abnormal Chichibabin pyridine synthesis. The generation of N-unsubstituted imine intermediates was also confirmed by formation of indole derivatives from alkyl azides. American Association for the Advancement of Science 2017-08-09 /pmc/articles/PMC5550227/ /pubmed/28808683 http://dx.doi.org/10.1126/sciadv.1700826 Text en Copyright © 2017 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC). http://creativecommons.org/licenses/by-nc/4.0/ This is an open-access article distributed under the terms of the Creative Commons Attribution-NonCommercial license (http://creativecommons.org/licenses/by-nc/4.0/) , which permits use, distribution, and reproduction in any medium, so long as the resultant use is not for commercial advantage and provided the original work is properly cited. |
spellingShingle | Research Articles Hu, Lu Liu, Yahu A. Liao, Xuebin In situ generation of N-unsubstituted imines from alkyl azides and their applications for imine transfer via copper catalysis |
title | In situ generation of N-unsubstituted imines from alkyl azides and their applications for imine transfer via copper catalysis |
title_full | In situ generation of N-unsubstituted imines from alkyl azides and their applications for imine transfer via copper catalysis |
title_fullStr | In situ generation of N-unsubstituted imines from alkyl azides and their applications for imine transfer via copper catalysis |
title_full_unstemmed | In situ generation of N-unsubstituted imines from alkyl azides and their applications for imine transfer via copper catalysis |
title_short | In situ generation of N-unsubstituted imines from alkyl azides and their applications for imine transfer via copper catalysis |
title_sort | in situ generation of n-unsubstituted imines from alkyl azides and their applications for imine transfer via copper catalysis |
topic | Research Articles |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5550227/ https://www.ncbi.nlm.nih.gov/pubmed/28808683 http://dx.doi.org/10.1126/sciadv.1700826 |
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