Organic Letters
Letter
K.; Akiyama, T. Angew. Chem., Int. Ed. 2011, 50, 8180−8183. (b) Wu,
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In summary, we have developed the first catalytic
asymmetric Mannich type reactions of β-ketocarbonyls with
CF3-, CF2H-, CCl3-, and C2F5-containing N,O-acetals
(NOAcs) by chiral primary amine catalysis. This reaction
provides a facile and efficient access to trifluoro- or
difluoroethyl amine and trichloroethyl amines in good yields
and with high enantioselectivity.
(4) For a review, see: (a) Waser, M.; Novacek, J. Angew. Chem., Int.
Ed. 2015, 54, 14228−14231 For selected examples, see: . (b) Wu, Y.;
Deng, L. J. Am. Chem. Soc. 2012, 134, 14334−14337. (c) Wu, Y.; Hu,
L.; Li, Z.; Deng, L. Nature 2015, 523, 445−450. (d) Zhou, X.; Wu, Y.;
Deng, L. J. Am. Chem. Soc. 2016, 138, 12297−12302. (e) Liu, M.; Li,
J.; Xiao, X.; Xie, Y.; Shi, Y. Chem. Commun. 2013, 49, 1404−1406.
(f) Su, J.; Ma, Z.; Li, X.; Lin, L.; Shen, Z.; Yang, P.; Li, Y.; Wang, H.;
Yan, W.; Wang, K.; Wang, R. Adv. Synth. Catal. 2016, 358, 3777−
3785.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
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S
Experimental procedures, characterization data, copies of
NMR spectra, and HPLC chart (PDF)
(5) For recent reviews on the Mannich reaction, see: (a) Notz, W.;
Tanaka, F.; Barbas, C. F., III Acc. Chem. Res. 2004, 37, 580−591.
Accession Codes
́
(b) Cordova, A. Acc. Chem. Res. 2004, 37, 102−112. (c) Liu, Y.; Wu,
CCDC 1863303 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
́
Q.; Yin, D.; Li, D. Youji Huaxue 2016, 36, 927−938. (d) Rosello, M.
S.; del Pozo, C.; Fustero, S. Synthesis 2016, 48, 2553−2571.
(e) Arrayas, R. G.; Carretero, J. C. Chem. Soc. Rev. 2009, 38,
1940−1948.
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(6) For selected examples of the Mannich reaction with chiral tri-/
difluoromethylimines, see: (a) Zhi, Y.; Zhao, K.; Liu, Q.; Wang, A.;
Enders, D. Chem. Commun. 2016, 52, 14011−14014. (b) Fioravanti,
S.; Mancinelli, F.; Parise, L.; Pelagalli, A.; Pellacani, L.; Trulli, L. RSC
Adv. 2016, 6, 101862−101868. (c) Pelagalli, A.; Pellacani, L.;
Fioravanti, S. Eur. J. Org. Chem. 2017, 2017, 3373−3380.
(d) Huguenot, F.; Brigaud, T. J. Org. Chem. 2006, 71, 2159−2162.
(e) Wu, L.; Xie, C.; Mei, H.; Dai, Y.; Han, J.; Soloshonok, V. A.; Pan,
AUTHOR INFORMATION
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Corresponding Author
ORCID
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Y. J. Org. Chem. 2015, 80, 3187−3194. (f) Fustero, S.; Ibanez, I.;
̃
Notes
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Barrio, P.; Maestro, M. A.; Catalan, S. Org. Lett. 2013, 15, 832−835.
(g) Shibata, N.; Nishimine, T.; Shibata, N.; Tokunaga, E.; Kawada,
K.; Kagawa, T.; Sorochinsky, A. E.; Soloshonok, V. A. Chem. Commun.
2012, 48, 4124−4126.
The authors declare no competing financial interest.
(7) You, Y.; Zhang, L.; Cui, L.; Mi, X.; Luo, S. Angew. Chem., Int. Ed.
2017, 56, 13814−13818.
ACKNOWLEDGMENTS
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We thank the Natural Science Foundation of China
(21390400, 21521002, 21572232, and 21672217), the Chinese
Academy of Science (QYZDJ-SSW-SLH023), and Tsinghua
University for financial support. S.L. is supported by the
National Program of Top-notch Young Professionals.
(8) (a) Muriel, B.; Orcel, U.; Waser, J. Org. Lett. 2017, 19, 3548−
3551. (b) Orcel, U.; Waser, J. Angew. Chem., Int. Ed. 2016, 55,
12881−12885. (c) Zard, S. Z.; Gagosz, F.; Laurich, D. Org. Synth.
2007, 84, 32−42.
(10) Zhang, L.; Fu, N.; Luo, S. Acc. Chem. Res. 2015, 48, 986−997.
(11) The slow rate of enamine formation as well as the instability of
the formed enamine under the present conditions may account for
this inactivity.
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