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Synthesis of difluoromethylated allenes through trifunctionalization of 1,3-enynes
Organofluorine compounds have shown their great value in many aspects. Moreover, allenes are also a class of important compounds. Fluorinated or fluoroalkylated allenes might provide an option as candidates for drug and material developments, as allenes allow a great number of valuable transformatio...
Autores principales: | , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6972827/ https://www.ncbi.nlm.nih.gov/pubmed/31964875 http://dx.doi.org/10.1038/s41467-019-14254-3 |
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author | Taj Muhammad, Munira Jiao, Yihang Ye, Changqing Chiou, Mong-Feng Israr, Muhammad Zhu, Xiaotao Li, Yajun Wen, Zhenhai Studer, Armido Bao, Hongli |
author_facet | Taj Muhammad, Munira Jiao, Yihang Ye, Changqing Chiou, Mong-Feng Israr, Muhammad Zhu, Xiaotao Li, Yajun Wen, Zhenhai Studer, Armido Bao, Hongli |
author_sort | Taj Muhammad, Munira |
collection | PubMed |
description | Organofluorine compounds have shown their great value in many aspects. Moreover, allenes are also a class of important compounds. Fluorinated or fluoroalkylated allenes might provide an option as candidates for drug and material developments, as allenes allow a great number of valuable transformations. Herein, we report a metal-free synthesis of difluoromethylated allenes via regioselective trifunctionalization of 1,3-enynes. This method proceeds through double C–F bond formation with concomitant introduction of an amino group to the allene. Synthetic applications are conducted and preliminary mechanistic studies suggest that a two-step pathway is involved. DFT calculations revealed an unusual dibenzenesulfonimide-assisted fluorination/fluoroamination with NFSI. In addition, kinetic reaction study revealed the induction period of both major and side products to support the proposed reaction mechanism. This work offers a convenient approach for the synthesis of a range of difluoromethylated allenes and is also a rare example of trifunctionalization of 1,3-enynes. |
format | Online Article Text |
id | pubmed-6972827 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-69728272020-01-22 Synthesis of difluoromethylated allenes through trifunctionalization of 1,3-enynes Taj Muhammad, Munira Jiao, Yihang Ye, Changqing Chiou, Mong-Feng Israr, Muhammad Zhu, Xiaotao Li, Yajun Wen, Zhenhai Studer, Armido Bao, Hongli Nat Commun Article Organofluorine compounds have shown their great value in many aspects. Moreover, allenes are also a class of important compounds. Fluorinated or fluoroalkylated allenes might provide an option as candidates for drug and material developments, as allenes allow a great number of valuable transformations. Herein, we report a metal-free synthesis of difluoromethylated allenes via regioselective trifunctionalization of 1,3-enynes. This method proceeds through double C–F bond formation with concomitant introduction of an amino group to the allene. Synthetic applications are conducted and preliminary mechanistic studies suggest that a two-step pathway is involved. DFT calculations revealed an unusual dibenzenesulfonimide-assisted fluorination/fluoroamination with NFSI. In addition, kinetic reaction study revealed the induction period of both major and side products to support the proposed reaction mechanism. This work offers a convenient approach for the synthesis of a range of difluoromethylated allenes and is also a rare example of trifunctionalization of 1,3-enynes. Nature Publishing Group UK 2020-01-21 /pmc/articles/PMC6972827/ /pubmed/31964875 http://dx.doi.org/10.1038/s41467-019-14254-3 Text en © The Author(s) 2020 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 Taj Muhammad, Munira Jiao, Yihang Ye, Changqing Chiou, Mong-Feng Israr, Muhammad Zhu, Xiaotao Li, Yajun Wen, Zhenhai Studer, Armido Bao, Hongli Synthesis of difluoromethylated allenes through trifunctionalization of 1,3-enynes |
title | Synthesis of difluoromethylated allenes through trifunctionalization of 1,3-enynes |
title_full | Synthesis of difluoromethylated allenes through trifunctionalization of 1,3-enynes |
title_fullStr | Synthesis of difluoromethylated allenes through trifunctionalization of 1,3-enynes |
title_full_unstemmed | Synthesis of difluoromethylated allenes through trifunctionalization of 1,3-enynes |
title_short | Synthesis of difluoromethylated allenes through trifunctionalization of 1,3-enynes |
title_sort | synthesis of difluoromethylated allenes through trifunctionalization of 1,3-enynes |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6972827/ https://www.ncbi.nlm.nih.gov/pubmed/31964875 http://dx.doi.org/10.1038/s41467-019-14254-3 |
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