Organic Letters
Letter
synthon) in the 1,5-hydride shift triggered Ugi-type reaction.
Notably, the reaction proceeds under mild conditions and
shows a tolerance to a broad scope of substrates, furnishing the
desired products in high atom economy and good yields.
Further exploration on the asymmetric synthesis of the
prolinamide and new synthetic applications involving dual
synthons is underway in our laboratory.
4260. (g) de Graaff, C.; Bensch, L.; van Lint, M. J.; Ruijter, E.; Orru, R.
V. A. Org. Biomol. Chem. 2015, 13, 10108.
(4) Dighe, S. U.; K. S., A. K.; Srivastava, S.; Shukla, P.; Singh, S.;
Dikshit, M.; Batra, S. J. Org. Chem. 2015, 80, 99.
(
(
5) Zhu, Z.; Seidel, D. Org. Lett. 2016, 18, 631.
6) For selected reviews, see: (a) Tobisu, M.; Chatani, N. Angew.
Chem., Int. Ed. 2006, 45, 1683. (b) Pan, S. C. Beilstein J. Org. Chem.
2012, 8, 1374. (c) Peng, B.; Maulide, N. Chem. - Eur. J. 2013, 19,
13274. (d) Haibach, M. C.; Seidel, D. Angew. Chem., Int. Ed. 2014, 53,
5010.
ASSOCIATED CONTENT
Supporting Information
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(7) (a) Kanishchev, M. I.; Shegolev, A. A.; Smit, W. A.; Caple, R.;
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S
Kelner, M. J. J. Am. Chem. Soc. 1979, 101, 5660. (b) Yoshimatsu, M.;
Hatae, N.; Shimizu, H.; Kataoka, T. Chem. Lett. 1993, 22, 1491.
(8) (a) Zhen, L.; Lin, C.; Du, H.-J.; Dai, L.; Wen, X.; Xu, Q.-L.; Sun,
H. Tetrahedron 2015, 71, 2839. (b) Zhen, L.; Dai, L.; Yu, S.-Q.; Lin,
C.; Sun, H.; Xu, Q.-L. Eur. J. Org. Chem. 2017, 2017, 560.
Experimental procedures and characterization data for all
X-ray data for compound 3a (CIF)
(9) Different electropositive fragments such as Michael acceptors,
iminium ions, aldehydes, and alkynes serving as hydride acceptors
participated in [1, 5]-hydride shift/C−H functionalization reactions.
(10) Guo, W.; Liao, J.; Liu, D.; Li, J.; Ji, F.; Wu, W.; Jiang, H. Angew.
AUTHOR INFORMATION
Chem., Int. Ed. 2017, 56, 1289.
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(11) (a) Du, H.-J.; Zhen, L.; Wen, X.; Xu, Q.-L.; Sun, H. Org. Biomol.
Chem. 2014, 12, 9716. (b) Jiang, C.-H.; Lei, X.; Zhen, L.; Du, H.-J.;
Wen, X.; Xu, Q.-L.; Sun, H. Beilstein J. Org. Chem. 2014, 10, 2892.
(c) Lei, X.; Xie, H.-Y.; Chen, S.-Y.; Teng, K.-S.; Wen, X.; Xu, Q.-L.;
Sun, H. Tetrahedron 2015, 71, 4098. (d) Chang, Y.-Z.; Li, M.-L.; Zhao,
W.-F.; Wen, X.; Sun, H.; Xu, Q.-L. J. Org. Chem. 2015, 80, 9620.
(12) We did not explore linear amines for our method, as most of the
previous methods used cyclic amines for 1,5-hydride shift. According
to the proposed mechanism, we speculated that linear amines should
be worse than cyclic amines for our reaction, since linear amines do
not have ring strain and their iminium intermediates are not as stable
as those generated from cyclic amines. Very recently, Suh et al.
ORCID
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
Financial support from National Natural Science Foundation of
China (Grants 81602966, 81530098, 81573299, 81473080, and
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1373303) is gratefully acknowledged. This project is also
supported by the Jiangsu Province Natural Science Foundation
BK20160759, BK20141355), the China “Creation of New
(
Drugs” Key Technology Projects (2015ZX09501001), and
Fundamental Research Funds for the Central Universities
(
2016ZPY013).
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