Synthesis of difluoromethylated allenes through trifunctionalization of 1,3-enynes
| Autor: | Changqing Ye, Mong-Feng Chiou, Yihang Jiao, Zhenhai Wen, Hongli Bao, Yajun Li, Munira Taj Muhammad, Muhammad Israr, Xiaotao Zhu, Armido Studer |
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| Jazyk: | angličtina |
| Rok vydání: | 2020 |
| Předmět: |
Reaction mechanism
Reaction mechanisms Induction period Allene Science General Physics and Astronomy Synthetic chemistry methodology 010402 general chemistry 01 natural sciences Article General Biochemistry Genetics and Molecular Biology chemistry.chemical_compound Stereochemistry Moiety lcsh:Science Multidisciplinary 010405 organic chemistry Regioselectivity General Chemistry Bond formation Combinatorial chemistry 0104 chemical sciences chemistry lcsh:Q Organofluorine compounds Material chemistry |
| Zdroj: | Nature Communications, Vol 11, Iss 1, Pp 1-8 (2020) Nature Communications |
| ISSN: | 2041-1723 |
| Popis: | 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. Fluorinated or fluoroalkylated allenes are versatile building blocks for medicinal and material chemistry. Here, the authors show a regioselective trifunctionalization of 1,3-enynes proceeding through double C-F bond formation and concomitant installation of a -NSO2Ph group to the allene moiety. |
| Databáze: | OpenAIRE |
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