Organic Letters
Letter
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synergistically and importantly positions the ketone moiety in
backside while (S) amide H bond and chiral phosphine direct the
pyridine in front side for the Re face attack to give the observed
(R) product under the steric effect of the aryl tethered PPh2
group.
In summary, we have developed 2-vinylpyridines as a new type
of activated alkene for enantioselective intermolecular cross R−
C reactions with 3-aroyl acrylates and 2-ene-1,4-diones. The
novel chiral phosphine catalysts containing amino acids were
designed to catalyze the cross asymmetric R−C reactions. The
process affords a new approach to synthetically valued chiral
pyridine building blocks. The studies expand the scope of the
challenging enantioselective intermolecular cross R−C reactions.
Further efforts aimed at the expansion of this novel activated
alkene chemistry to other transformations are currently under-
way in our laboratories.
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ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
Experimental details and spectroscopic data (PDF)
Accession Codes
(14) For selected examples of intermolecular R−C reactions, see:
(a) Reynolds, T. E.; Binkley, M. S.; Scheidt, K. A. Org. Lett. 2008, 10,
2449. (b) Li, S.; Liu, Y.; Huang, B.; Zhou, T.; Tao, H.; Xiao, Y.; Liu, L.;
Zhang, J. ACS Catal. 2017, 7, 2805. (c) Shi, Z.; Yu, P.; Loh, T.-P.; Zhong,
G. Angew. Chem., Int. Ed. 2012, 51, 7825. (d) Shi, Z.; Loh, T.-P. Angew.
Chem., Int. Ed. 2013, 52, 8584. (e) Gao, Y.; Xu, Q.; Wei, Y.; Shi, M. Adv.
Synth. Catal. 2017, 359, 1663. (f) Zhang, X.; Gan, K.; Liu, X.; Deng, Y.;
Wang, F.; Yu, K.; Zhang, J.; Fan, C. Org. Lett. 2017, 19, 3207.
(15) Examples of intramolecular asymmetric R−C reaction:
(a) Aroyan, C. E.; Miller, S. J. J. Am. Chem. Soc. 2007, 129, 256.
(b) Su, X.; Zhou, W.; Li, Y.; Zhang, J. Angew. Chem., Int. Ed. 2015, 54,
6874. (c) Yao, W.; Dou, X.; Wen, S.; Wu, J.; Vittal, J. J.; Lu, Y. Nat.
Commun. 2016, 7, 13024.
CCDC 1585391 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge via
Crystallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION
Corresponding Authors
■
ORCID
(16) Zhao, Q.; Pei, C.; Guan, X.; Shi, M. Adv. Synth. Catal. 2011, 353,
1973.
(17) Dong, X.; Liang, L.; Li, E.; Huang, Y. Angew. Chem., Int. Ed. 2015,
54, 1621.
Notes
(18) Zhou, W.; Su, X.; Tao, M.; Zhu, C.; Zhao, Q.; Zhang, J. Angew.
Chem., Int. Ed. 2015, 54, 14853.
The authors declare no competing financial interest.
(19) For reviews related to chiral phosphine catalysis, see: (a) Ye, L.-
W.; Zhou, J.; Tang, Y. Chem. Soc. Rev. 2008, 37, 1140. (b) Wei, Y.; Shi,
M. Acc. Chem. Res. 2010, 43, 1005. (c) Wei, Y.; Shi, M. Chem. Rev. 2013,
113, 6659. (d) Wang, Z.; Xu, X.; Kwon, O. Chem. Soc. Rev. 2014, 43,
2927. (e) Li, W.; Zhang, J. Chem. Soc. Rev. 2016, 45, 1657.
(20) (a) Li, T.; Zhu, J.; Wu, D.; Li, X.; Wang, S.; Li, H.; Li, J.; Wang, W.
Chem. - Eur. J. 2013, 19, 9147. (b) Li, X.; Wang, S.; Li, T.; Li, J.; Li, H.;
Wang, W. Org. Lett. 2013, 15, 5634. (c) Yu, Y.; Liu, Y.; Liu, A.; Xie, H.;
Li, H.; Wang, W. Org. Biomol. Chem. 2016, 14, 7455. (d) Li, H.; Li, X.;
Yu, Y.; Li, J.; Liu, Y.; Li, H.; Wang, W. Org. Lett. 2017, 19, 2010. (e) Li, J.;
Qin, C.; Yu, Y.; Fan, H.; Fu, Y.; Li, H.; Wang, W. Adv. Synth. Catal. 2017,
359, 2191.
ACKNOWLEDGMENTS
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This work was supported by the National Natural Science
Foundation of China (21572055, 21738002, and 21572054), the
program for Professor of Special Appointment (Eastern Scholar)
at Shanghai Institutions of Higher Learning, and the
Fundamental Research Funds for the Central Universities.
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