Organic Letters
Letter
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reagent. Based on these results, a plausible mechanism with
radical type intermediates was proposed for the titled reaction
(see Scheme 6c).3 Single-electron transfer (SET) from zinc to
the NHP ester would result in fragmentation of the radical
anion A to a stabilized NHP− anion and a carboxyl radical,
which readily undergo a Barton decarboxylation to generate
the R• radical. The gem-difluoroalkene would undergo a
nucleophilic attack by radical R•, to afford radical intermediate
B that is reduced by Zn+ to anion C in a second SET process.
Extrusion of a fluoride from C via a conformationally favorable
anticoplanar pathway would give the Z-monofluoroalkene 3.
In summary, a mild, scalable, and general method has been
developed for the decarboxylative defluoroalkylation of gem-
difluoroalkenes with NHP esters using zinc powder as the
reductant, to furnish a wide range of monofluoroalkenes in
good to high yields and excellent Z-selectivities. The reaction
tolerates a broad scope of functional groups and can be easily
scaled up, which hold promise for practical synthetic
applications. Preliminary mechanistic studies strongly sup-
ported the radical nature of the reaction. Further studies are
underway in our laboratories.
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ASSOCIATED CONTENT
* Supporting Information
■
(g) Zell, D.; Dhawa, U.; Muller, V.; Bursch, M.; Grimme, S.;
̈
S
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The Supporting Information is available free of charge on the
Experimental procedure, characterization of all new
compounds and results of in situ NMR (PDF)
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Accession Codes
CCDC 1832289 contain the supplementary crystallographic
data for this paper. These data can be obtained free of charge
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, U.K.; fax: + 44 1223 336033.
AUTHOR INFORMATION
■
Corresponding Author
ORCID
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
Financial support was provided by the National Natural
Science Foundation of China (No. 81673297) and the
Shanghai Municipal Committee of Science and Technology
(Nos. 17JC1400200 and 17431902500).
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