Journal of the American Chemical Society
ARTICLE
mechanistic survey, including NMR and computational studies
in concert with rationalization of the preferred reaction pathway
and the origin of stereoselectivity, has been presented. Further-
more, we have illustrated that trienamine catalysis can be merged
with other amino-catalyzed activation modes, as demonstrated
by the first trienamineꢀenamine tandem reaction. We believe
that this work may open up for new possibilities of trienamine
catalyzed cycloadditions and tandem reactions, offering an
interesting entry to complex molecule synthesis using asym-
metric catalysis.
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’ ASSOCIATED CONTENT
S
Supporting Information. Complete experimental proce-
b
dures and characterization (PDF). This material is available free
(7) For seminal work, see: (a) Ahrendt, K. A.; Borths, C. J.;
MacMillan, D. W. C. J. Am. Chem. Soc. 2000, 122, 4243. For other
selected examples, see e.g.:(b) Brandau, S.; Landa, A.; Franzꢀen, J.;
Marigo, M.; Jørgensen, K. A. Angew. Chem., Int. Ed. 2006, 45, 4305.
(c) Gotoh, H.; Masui, R.; Ogino, H.; Shoji, M.; Hayashi, Y. Angew.
Chem., Int. Ed. 2006, 45, 6853. (d) Ouellet, S. G.; Tuttle, J. B.;
MacMillan, D. W. C. J. Am. Chem. Soc. 2005, 127, 32. (e) Mayer, S.;
List, B. Angew. Chem., Int. Ed. 2006, 45, 4193. (f) Wang, W.; Li, H.;
Wang, J.; Zu, L. J. Am. Chem. Soc. 2006, 128, 10354. (g) Rios, R.; Sundꢀen,
H.; Ibrahem, I.; Zhao, G.; Eriksson, L.; Cꢀordova, A. Tetrahedron Lett.
2006, 47, 8547. (h) Jiang, H.; Nielsen, J. B.; Nielsen, M.; Jørgensen, K. A.
Chem.—Eur. J. 2007, 13, 9068. (i) Chen, Y. K.; Yoshida, M.; MacMillan,
D. W. C. J. Am. Chem. Soc. 2006, 128, 9328. (j) Ibrahem, I.; Rios, R.;
Vesely, J.; Zhao, G.; Cꢀordova, A. Chem. Commun. 2007, 8, 849. (k)
Bertelsen, S.; Dinꢀer, P.; Johansen, R. L.; Jørgensen, K. A. J. Am. Chem.
Soc. 2007, 129, 1536. (l) Jiang, K.; Jia, Z.-J.; Yin, X.; Wu, L.; Chen, Y.-C.
Org. Lett. 2010, 12, 2766.
’ AUTHOR INFORMATION
Corresponding Author
ycchenhuaxi@yahoo.com.cn; kaj@chem.au.dk
’ ACKNOWLEDGMENT
We acknowledge financial support from the Carlsberg Foun-
dation and OChem Graduate School. B.G. thanks The Swiss
National Science Foundation for support, and Y.C.C. thanks the
Natural Science Foundation of China (20972101 and 21021001)
and National Basic Research Program of China (973 Program)
(2010CB833300) for financial support.
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Please note that the provided calculations only account for the ground
state energies for the three rotamers and the activation barriers for their
interconversions.
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