7094; (d) F. W. Patureau and F. Glorius, J. Am. Chem. Soc., 2010, 132,
9982; (e) F. W. Patureau, T. Besset and F. Glorius, Angew. Chem., Int.
Ed., 2011, 50, 1064; (f) A. S. Tsai, M. Brasse, R. G. Bergman and J. A.
Ellman, Org. Lett., 2011, 13, 540; (g) F. Wang, G. Song, Z. Du and X.
Li, J. Org. Chem., 2011, 76, 2926. For Rh(III)-catalyzed alkynylations
of our group, see: (h) S. Rakshit, F. W. Patureau and F. Glorius, J. Am.
Chem. Soc., 2010, 132, 9585; (i) F. W. Patureau, T. Besset, N. Kuhl and
F. Glorius, J. Am. Chem. Soc., 2011, 133, 2154.
6 For rare Ru-catalyzed examples of oxidative C–H olefination, see: (a) H.
Weissman, X. Song and D. Milstein, J. Am. Chem. Soc., 2001, 123, 337;
(b) T. Ueyama, S. Mochida, T. Fukutani, K. Hirano, T. Satoh and M.
Miura, Org. Lett., 2011, 13, 706.
7 For a recent minireview on internal oxidants in C–H bond activation
processes, see: F. W. Patureau and F. Glorius, Angew. Chem., Int. Ed.,
2011, 50, 1977.
8 J. Wu, L. Chen, G. Jang, X. Cui and Y. Wu, J. Am. Chem. Soc., 2009,
131, 13888.
(5)
In conclusion, the reported olefination–Michael addition tan-
dem process proceeds in a highly regioselective manner under mild
conditions using an organic oxidant exhibiting a broad functional
group tolerance. N-Methoxy-N¢-aryl ureas were found to be
superior oxidants compared to a variety of organic and metal-
lic oxidants. Our mechanistic investigation including deuterium
labelling experiments further shed light on the intermediates
involved in the catalytic cycle.
9 Y. Tan and J. F. Hartwig, J. Am. Chem. Soc., 2010, 132, 3676.
10 K. H. Ng, A. S. C. Chan and W.-Y. Yu, J. Am. Chem. Soc., 2010, 132,
12862.
11 P. C. Too, Y.-F. Wang and S. Chiba, Org. Lett., 2010, 12, 5688.
12 (a) N. Guimond, C. Gouliaras and K. Fagnou, J. Am. Chem. Soc.,
2010, 132, 6908; (b) N. Guimond, S. I. Gorelsky and K. Fagnou, J. Am.
Chem. Soc., 2011, 133, 6449.
Acknowledgements
Generous financial support by the Studienstiftung des deutschen
Volkes (JW) and the NRW Graduate School of Chemistry (SR) is
gratefully acknowledged. We thank Fan Liu and Thomas Dro¨ge
for helpful discussions. The research of FG was supported by the
Alfried Krupp Prize for Young University Teachers of the Alfried
Krupp von Bohlen und Halbach Foundation.
13 S. Rakshit, C. Grohmann, T. Besset and F. Glorius, J. Am. Chem. Soc.,
2011, 133, 2350.
14 For the use of N-methoxyamides as directing groups, see: (a) D.-H.
Wang, M. Wasa, R. Giri and J.-Q. Yu, J. Am. Chem. Soc., 2008, 130,
7190; (b) M. Wasa and J.-Q. Yu, J. Am. Chem. Soc., 2008, 130, 14058.
15 For the use of ureas as directing groups in C–H bond activation, see:
(a) C. E. Houlden, C. D. Bailey, J. G. Ford, M. R. Gagne´, G. C. Lloyd-
Jones and K. I. Booker-Milburn, J. Am. Chem. Soc., 2008, 130, 10066;
(b) M. P. Huestis, L. Chan, D. R. Stuart and K. Fagnou, Angew. Chem.,
Int. Ed., 2011, 50, 1338.
16 Examples of tandem C–H olefination–Michael addition reports:
(a) Ref. 5a–b; (b) F. Wang, G. Song and X. Li, Org. Lett., 2010, 12,
5430; (c) M. Wasa, K. M. Engle and J.-Q. Yu, J. Am. Chem. Soc., 2010,
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