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Transition metal-free intramolecular regioselective couplings of aliphatic and aromatic C-H bonds
Cross-dehydrogenative couplings of two different C-H bonds have emerged as an attractive goal in organic synthesis. However, achieving regioselective C-H activation is a great challenge because C-H bonds are ubiquitous in organic compounds. Actually, the regioselective couplings promoted by enzymes...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group
2016
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4731807/ https://www.ncbi.nlm.nih.gov/pubmed/26822836 http://dx.doi.org/10.1038/srep19931 |
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author | Tian, Hua Yang, Haijun Zhu, Changjin Fu, Hua |
author_facet | Tian, Hua Yang, Haijun Zhu, Changjin Fu, Hua |
author_sort | Tian, Hua |
collection | PubMed |
description | Cross-dehydrogenative couplings of two different C-H bonds have emerged as an attractive goal in organic synthesis. However, achieving regioselective C-H activation is a great challenge because C-H bonds are ubiquitous in organic compounds. Actually, the regioselective couplings promoted by enzymes are a common occurrence in nature. Herein, we have developed simple, efficient and general transition metal-free intramolecular couplings of alphatic and aromatic C-H bonds. The protocol uses readily available aryl triazene as the radical initiator, cheap K(2)S(2)O(8) as the oxidant, and the couplings were performed well with excellent tolerance of functional groups. Interestingly, α-carbon configuration of some amino acid residues in the substrates was kept after the reactions, and the couplings for substrates with substituted phenylalanine residues exhibited complete β-carbon diastereoselectivity for induction of the chiral α-carbon. Therefore, the present study should provide a novel strategy for regioselective cross-dehydrogenative couplings of two different C-H bonds. |
format | Online Article Text |
id | pubmed-4731807 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2016 |
publisher | Nature Publishing Group |
record_format | MEDLINE/PubMed |
spelling | pubmed-47318072016-02-04 Transition metal-free intramolecular regioselective couplings of aliphatic and aromatic C-H bonds Tian, Hua Yang, Haijun Zhu, Changjin Fu, Hua Sci Rep Article Cross-dehydrogenative couplings of two different C-H bonds have emerged as an attractive goal in organic synthesis. However, achieving regioselective C-H activation is a great challenge because C-H bonds are ubiquitous in organic compounds. Actually, the regioselective couplings promoted by enzymes are a common occurrence in nature. Herein, we have developed simple, efficient and general transition metal-free intramolecular couplings of alphatic and aromatic C-H bonds. The protocol uses readily available aryl triazene as the radical initiator, cheap K(2)S(2)O(8) as the oxidant, and the couplings were performed well with excellent tolerance of functional groups. Interestingly, α-carbon configuration of some amino acid residues in the substrates was kept after the reactions, and the couplings for substrates with substituted phenylalanine residues exhibited complete β-carbon diastereoselectivity for induction of the chiral α-carbon. Therefore, the present study should provide a novel strategy for regioselective cross-dehydrogenative couplings of two different C-H bonds. Nature Publishing Group 2016-01-29 /pmc/articles/PMC4731807/ /pubmed/26822836 http://dx.doi.org/10.1038/srep19931 Text en Copyright © 2016, Macmillan Publishers Limited http://creativecommons.org/licenses/by/4.0/ This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ |
spellingShingle | Article Tian, Hua Yang, Haijun Zhu, Changjin Fu, Hua Transition metal-free intramolecular regioselective couplings of aliphatic and aromatic C-H bonds |
title | Transition metal-free intramolecular regioselective couplings of aliphatic and aromatic C-H bonds |
title_full | Transition metal-free intramolecular regioselective couplings of aliphatic and aromatic C-H bonds |
title_fullStr | Transition metal-free intramolecular regioselective couplings of aliphatic and aromatic C-H bonds |
title_full_unstemmed | Transition metal-free intramolecular regioselective couplings of aliphatic and aromatic C-H bonds |
title_short | Transition metal-free intramolecular regioselective couplings of aliphatic and aromatic C-H bonds |
title_sort | transition metal-free intramolecular regioselective couplings of aliphatic and aromatic c-h bonds |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4731807/ https://www.ncbi.nlm.nih.gov/pubmed/26822836 http://dx.doi.org/10.1038/srep19931 |
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