Organic Letters
Letter
(b) Schroder, N.; Wencel-Delord, J.; Glorius, F. J. Am. Chem. Soc. 2012,
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these preliminary results will find broad synthetic utility and
boost the development of novel methods for creating C−halogen
moieties in the unactivated remote C(sp3)−H bonds.
(8) For sp3 C−H functionalization in organic synthesis, see:
(a) McMurray, L.; O’Hara, F.; Gaunt, M. J. Chem. Soc. Rev. 2011, 40,
1885. (b) Gutekunst, W. R.; Baran, P. S. Chem. Soc. Rev. 2011, 40, 1976
and references cited therein.
ASSOCIATED CONTENT
* Supporting Information
(9) (a) Wheelaghan, O. R.; Ortuno, M. A.; Díez, J.; Garrido, S. E. G.;
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Maya, C.; Lledos, A.; Conejero, S. J. Am. Chem. Soc. 2012, 134, 15261.
S
(b) Crosby, S. H.; Thomas, H. R.; Clarkson, G. J.; Rourke, J. P. Chem.
Commun. 2012, 48, 5775. (c) Kaspi, A. W.; Goldberg, I.; Vigalok, A. J.
Am. Chem. Soc. 2010, 132, 10626. (d) Oloo, W.; Zavalij, P. Y.; Zhang, J.;
Khaskin, E.; Vedernikov, A. N. J. Am. Chem. Soc. 2010, 132, 14400.
(e) Frech, C. M.; Milstein, D. J. Am. Chem. Soc. 2006, 128, 12434.
(f) Goldberg, K. I.; Yan, J. Y.; Winter, E. L. J. Am. Chem. Soc. 1994, 116,
1573.
Detailed experimental procedures and spectra. This material is
AUTHOR INFORMATION
Corresponding Author
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Notes
(10) (a) Roy, A. H.; Hartwig, J. F. Organometallics 2004, 23, 1533.
(b) Canty, A. J. Acc. Chem. Res. 1992, 25, 83.
(11) (a) Rit, R. K.; Yadav, M. R.; Sahoo, A. K. Org. Lett. 2012, 14, 3724.
(b) Rit, R. K.; Yadav, M. R.; Sahoo, A. K. Org. Lett. 2014, 16, 968.
(12) For more details, see the Supporting Information.
The authors declare no competing financial interest.
DEDICATION
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(13) The exact role of bidentate MPyS-DG for the C(sp3)−H
halogenation is not known. Both the N-atoms in MPyS-DG are sp2-
hybridized, while other bidentate DGs in 5d−g possess one sp2-N-atom.
Although the strong binding affinity of N-atoms in 5d−g successfully
activates the C(sp3)−H bond, it presumably hampers the ready
reductive elimination under the optimized conditions. Whereas the
weak coordination of the sulfoximine N(sp2)-atom to metal facilitates
reductive elimination.
Dedicated to Professor H. Ila on the occasion of her 70th
birthday.
ACKNOWLEDGMENTS
This research was supported by the SERB, India. R.K.R., M.R.Y.,
K.G., and M.S. thank CSIR, India for a fellowship.
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(14) Djerassi, C. Chem. Rev. 1948, 43, 271.
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