Journal of the American Chemical Society
Communication
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direct nucleophilic bromodifluoromethylation of the highly reactive
1,3-dimethylimidazolidine-2,4,5-trione with TMSCF2Br was reported
by Geffken and coworkers as early as 1990, similar reactions with
simple aldehydes or ketones have not been achieved to date. We also
tried the reaction of TMSCF2Br and aldehydes with tetrabutylammo-
nium triphenyldifluorosilicate as the nucleophilic catalyst, but no
desired product was observed.
However, this observation can be partially rationalized by the
sterically congested environment around the N and O donors.
It is also somewhat surprising that halogen−π interactions
between the halocarbon and the heteroaromatic donor were
observed in compound 3c.
In summary, we have reported the unprecedented iodo- and
bromodifluoromethylation reactions of carbonyl compounds
through a new synthetic strategy, namely, halogenation of the
in situ-generated sulfinate intermediates in the Julia−Kocienski
reaction to change the reaction pathway from olefination to
alkylation. A wide range of aldehydes and ketones were
subjected to the present method to give the corresponding
iodo- and bromodifluoromethylated products in high yields.
Halogen−π interactions between the halocarbon and aromatic
donors were observed in the crystal structures of the products.
The method could also be extended to the introduction of
other fluorinated groups, such as −CFClBr, −CFClI, −CFBr2,
and −CFMeI, which opens up a new avenue for the synthesis
of a wide range of useful fluorinated compounds. The
“hijacking” of the sulfinate intermediates in the Julia−Kocienski
reaction for other synthetic applications has been largely
ignored in the past, and our work adds new possibilities for
further elaboration of this classical reaction.
ASSOCIATED CONTENT
* Supporting Information
■
S
Experimental procedures, characterization data for all new
compounds, and crystallographic data for 3c, 13, and 15 (CIF).
This material is available free of charge via the Internet at
(8) Wang, F.; Zhang, W.; Zhu, J.; Li, H.; Huang, K.-W.; Hu, J. Chem.
Commun. 2011, 47, 2411.
(9) Huang, W. Y.; Huang, B. N.; Hu, C. M. J. Fluorine Chem. 1983,
23, 193.
AUTHOR INFORMATION
Corresponding Author
■
(10) Cao, H.-P.; Chen, Q.-Y. J. Fluorine Chem. 2007, 128, 1187.
(11) For reviews of Julia−Kocienski olefination, see: (a) Aissa, C.
Eur. J. Org. Chem. 2009, 1831. (b) Blakemore, P. R. J. Chem. Soc.,
Perkin Trans. 1 2002, 2565. (c) Ma, J.; Wang, F.; Wang, J.; You, Q.
Chin. J. Org. Chem. 2010, 30, 1615.
(12) Plesniak, K.; Zarecki, A.; Wicha, J. In Sulfur-Mediated
Rearrangements II; Schaumann, E., Ed.; Springer: New York, 2007.
(13) (a) Zhao, Y.; Huang, W.; Zhu, L.; Hu, J. Org. Lett. 2010, 12,
1444. (b) Prakash, Olah and co-workers also reported the use of
reagent 1 in the synthesis of difluorinated alkanesulfonates. See:
Prakash, G. K. S.; Ni, C.; Wang, F.; Hu, J.; Olah, G. A. Angew. Chem.,
Int. Ed. 2011, 50, 2559.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the National Natural Science
Foundation of China (20825209, 20832008), the National
Basic Research Program of China (2012CB215500), and the
Chinese Academy of Sciences. Y.Z. thanks Jian Lu (University
̈
of Nottingham) for helpful discussions and processing of Figure
1. J.H. thanks Dr. Jun Xiao (Henkel Corporation) for helpful
discussions.
(14) Braun, M.-G.; Quiclet-Sire, B.; Zard, S. Z. J. Am. Chem. Soc.
2011, 133, 15954.
(15) Halogen Bonding: Fundamentals and Applications; Metrangolo,
P., Resnati, G., Ed.; Springer: New York, 2007.
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