Journal of the American Chemical Society
Communication
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In summary, we have reported the first example of a dynamic
kinetic asymmetric [3 + 2] annulation reaction of aminocyclo-
propanes. The reaction proceeded with high enantio- and
diastereoselectivity with a broad range of acyclic alkyl enol ethers
and aldehydes using a Cu catalyst with a commercially available
bisoxazoline ligand. Importantly, the developed catalytic system
could be used for both types of substrates without reoptimiza-
tion. The method is expected to be highly useful for the
asymmetric synthesis of nitrogen-rich small organic molecules.
(7) Steinreiber, J.; Faber, K.; Griengl, H. Chem.Eur. J. 2008, 14, 8060.
(8) DYKAT: (a) Parsons, A. T.; Johnson, J. S. J. Am. Chem. Soc. 2009,
131, 3122. (b) Parsons, A. T.; Smith, A. G.; Neel, A. J.; Johnson, J. S. J.
Am. Chem. Soc. 2010, 132, 9688. (c) Wales, S. M.; Walker, M. M.;
Johnson, J. S. Org. Lett. 2013, 15, 2558. (d) Trost, B. M.; Morris, P. J.
Angew. Chem., Int. Ed. 2011, 50, 6167. (e) Trost, B. M.; Morris, P. J.;
Sprague, S. J. J. Am. Chem. Soc. 2012, 134, 17823. (f) Mei, L. Y.; Wei, Y.;
Xu, Q.; Shi, M. Organometallics 2012, 31, 7591. (g) Mei, L. Y.; Wei, Y.;
Xu, Q.; Shi, M. Organometallics 2013, 32, 3544. (h) Xu, H.; Qu, J. P.;
Liao, S. H.; Xiong, H.; Tang, Y. Angew. Chem., Int. Ed. 2013, 52, 4004.
Only the examples based on cyclopropanes as limiting substrates are
listed. Kinetic resolutions and other asymmetric transformations:
(i) Sibi, M. P.; Ma, Z. H.; Jasperse, C. P. J. Am. Chem. Soc. 2005, 127,
5764. (j) Kang, Y. B.; Sun, X. L.; Tang, Y. Angew. Chem., Int. Ed. 2007, 46,
3918. (k) Zhou, Y. Y.; Wang, L. J.; Li, J.; Sun, X. L.; Tang, Y. J. Am. Chem.
Soc. 2012, 134, 9066. (l) Zhou, Y. Y.; Li, J.; Ling, L.; Liao, S. H.; Sun, X.
L.; Li, Y. X.; Wang, L. J.; Tang, Y. Angew. Chem., Int. Ed. 2013, 52, 1452.
(m) Xiong, H.; Xu, H.; Liao, S. H.; Xie, Z. W.; Tang, Y. J. Am. Chem. Soc.
2013, 135, 7851. (n) Moran, J.; Smith, A. G.; Carris, R. M.; Johnson, J.
S.; Krische, M. J. J. Am. Chem. Soc. 2011, 133, 18618.
(9) The enol ethers and cyclopropanes used in this study were
synthesized using modified reported procedures: Enol ethers: (a) Bosch,
M.; Schlaf, M. J. Org. Chem. 2003, 68, 5225. Cyclopropanes: (b) Bayer,
E.; Geckeler, K. Angew. Chem., Int. Ed. 1979, 18, 533. (c) Baret, N.;
Dulcere, J. P.; Rodriguez, J.; Pons, J. M.; Faure, R. Eur. J. Org. Chem.
2000, 1507. (d) Kacprzak, K. Synth. Commun. 2003, 33, 1499. (e) Wyatt,
P.; Hudson, A.; Charmant, J.; Orpen, A. G.; Phetmung, H. Org. Biomol.
Chem. 2006, 4, 2218. (f) Gonzalez-Bobes, F.; Fenster, M. D. B.; Kiau, S.;
Kolla, L.; Kolotuchin, S.; Soumeillant, M. Adv. Synth. Catal. 2008, 350,
813. See Supporting Information (SI) for detailed procedures.
(10) For easier comparison, the values given in Scheme 2C have been
limited to those obtained when changing a single parameter from the
optimized conditions given in Scheme 2B. For the optimization studies,
the yields and diastereoselectivities were calculated by NMR and the er
was determined by chiral HPLC; see SI for further details.
ASSOCIATED CONTENT
* Supporting Information
■
S
Experimental procedures and analytical data for all new
compounds. This material is available free of charge via the
AUTHOR INFORMATION
Corresponding Author
■
Author Contributions
‡F.d.N. and E.S. contributed equally.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank F. Hoffmann-La Roche Ltd. for an unrestricted
research grant and the Swiss National Science Foundation
(SNSF, Grant Numbers 200021_129874 and 200020_149494)
for financial support. We thank Mr. Kurt Schenk of the Institute
of the Physics of Biological Systems at EPFL for the X-ray
studies.
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(11) See Figure S1 in the Supporting Information.
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