Organic Letters
Letter
indicates that the fluorine and 2-pyridyl group are necessary to
Jinlong Zhang − State Key Laboratory for Oxo Synthesis and
Selective Oxidation, Center for Excellence in Molecular
Synthesis, Suzhou Research Institute of LICP, Lanzhou Institute
of Chemical Physics (LICP), Chinese Academy of Sciences,
Lanzhou 730000, People’s Republic of China
Huameng Yang − State Key Laboratory for Oxo Synthesis and
Selective Oxidation, Center for Excellence in Molecular
Synthesis, Suzhou Research Institute of LICP, Lanzhou Institute
of Chemical Physics (LICP), Chinese Academy of Sciences,
Lanzhou 730000, People’s Republic of China
this transformation. Taken together, these results suggest that
2
2
these intramolecular Csp −Csp coupling products are generated
2
2
by desulfonylation and intramolecular Csp −Csp coupling
concerted reaction pathways. Meanwhile, the elimination of
hydrogen fluoride and C−S bond cleavage paths are the major
side reaction processes.
In summary, we have developed the first Grignard-reagents-
2
2
activated desulfonylation/intramolecular Csp −Csp coupling of
α-fluoro-α,β-unsaturated-(2-pyridyl)sulfone to synthesize 2-(1-
fluorovinyl)pyridines. Preliminary mechanistic investigations
disclose that the introduction of fluorine should reduce the
electrophilicity of the β-carbon via the “negative fluorine
effect” and the coordination of magnesium to nitrogen could
activate the 2-position of the pyridine ring to make the reaction
occur. The current method is complementary to the
transformation of unsaturated sulfones and represents a
valuable addition to the synthetic toolbox for organofluorine
chemistry. Our study not only provides a new protocol to
obtain 2-(1-fluorovinyl)pyridines but also gives new insights
into the new reactivity of fluoride unsaturated-(2-pyridyl)-
sulfones without a transition-metal catalyst. Further study in
this direction is underway in our laboratory.
Complete contact information is available at:
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
Financial support from the National Natural Science
Foundation of China (No. 21602231), Chinese Academy of
Sciences “Light of West China” Program, and the Natural
Science Foundation of Jiangsu Province (Nos. BK20160396
and BK20191197) is gratefully acknowledged.
ASSOCIATED CONTENT
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REFERENCES
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* Supporting Information
The Supporting Information is available free of charge at
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Experimental procedures and spectral data (PDF)
Accession Codes
CCDC 2024903 contains the supplementary crystallographic
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bridge Crystallographic Data Centre, 12 Union Road,
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Corresponding Authors
Jinlong Qian − State Key Laboratory for Oxo Synthesis and
Selective Oxidation, Center for Excellence in Molecular
Synthesis, Suzhou Research Institute of LICP, Lanzhou Institute
of Chemical Physics (LICP), Chinese Academy of Sciences,
Lanzhou 730000, People’s Republic of China; orcid.org/
Gaoxi Jiang − State Key Laboratory for Oxo Synthesis and
Selective Oxidation, Center for Excellence in Molecular
Synthesis, Suzhou Research Institute of LICP, Lanzhou Institute
of Chemical Physics (LICP), Chinese Academy of Sciences,
Lanzhou 730000, People’s Republic of China; orcid.org/
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Authors
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Lei Kang − State Key Laboratory for Oxo Synthesis and Selective
Oxidation, Center for Excellence in Molecular Synthesis, Suzhou
Research Institute of LICP, Lanzhou Institute of Chemical
Physics (LICP), Chinese Academy of Sciences, Lanzhou
730000, People’s Republic of China; University of Chinese
Academy of Sciences, Beijing 100049, People’s Republic of
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