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...

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Published in:Nature communications 2020-01, Vol.11 (1), p.416-416, Article 416
Main Authors: Taj Muhammad, Munira, Jiao, Yihang, Ye, Changqing, Chiou, Mong-Feng, Israr, Muhammad, Zhu, Xiaotao, Li, Yajun, Wen, Zhenhai, Studer, Armido, Bao, Hongli
Format: Article
Language:English
Subjects:
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Allene
Bonding
Chemical bonds
Fluorination
Humanities and Social Sciences
Hydrocarbons
Laboratories
Ligands
multidisciplinary
Organic chemistry
Organofluorine compounds
Reaction mechanisms
Regioselectivity
Science
Science (multidisciplinary)
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Summary: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 -NSO 2 Ph group to the allene moiety.
ISSN:2041-1723
2041-1723
DOI:10.1038/s41467-019-14254-3