Organic Letters
Letter
Chen, Q.-Y.; Guo, Y.; Xiao, J.-C.; Gu, Y.-C. Coord. Chem. Rev. 2014,
261, 28−72.
give the trifluoromethylation product, probably due to the
interception of F− by TMS, which would then impede the
combination of F− and :CF2.
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In summary, we have found that difluorocarbene derived
from various carbene precursors could be decomposed by DBU
and further converted to a trifluoromethyl anion without the
addition of an external fluoride ion. Mechanistic investigation
revealed the detailed difluorocarbene conversion process in
which the decomposed difluorocarbene was finally transformed
into a fluoride ion and carbon monoxide. This process was
successfully applied in the trifluoromethylation of a variety of
(hetero)aromatic iodides, which might convert many difluor-
ocarbene precursors into efficient trifluoromethylation reagents.
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ASSOCIATED CONTENT
* Supporting Information
■
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S
Experimental procedures, analytical data for products, NMR
spectra of products. This material is available free of charge via
́
(d) Tomashenko, O. A.; Escudero-Adan, E. C.; Belmonte, M. M.;
Grushin, V. V. Angew. Chem., Int. Ed. 2011, 50, 7655−7659.
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AUTHOR INFORMATION
Corresponding Author
■
Notes
(18) Mehta, V. P.; Greaney, M. F. Org. Lett. 2013, 15, 5036−5039.
(19) Oshiro, K.; Morimoto, Y.; Amii, H. Synthesis 2010, 2080−2084.
(20) Wang, F.; Zhang, W.; Zhu, J.; Li, H.; Huang, K.-W.; Hu, J. Chem.
Commun. 2011, 47, 2411−2413.
(21) Li, L.; Wang, F.; Ni, C.; Hu, J. Angew. Chem., Int. Ed. 2013, 52,
12390−12394.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was financially supported by the National Natural
Science Foundation (21032006, 21172240, 21421002,
21472222), National Basic Research Program of China
(2015CB931900), and the Chinese Academy of Sciences. We
thank Dr. Xiao-Wen Huang (Shandong University of Science
and Technology) for helpful discussions.
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