Organic Letters
Letter
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palladium−alkenyl bond of C′ leads to the formation of acyl
palladium complex D. Intramolecular aminolysis eventually
furnishes the observed product along with regeneration of the
active palladium hydride species for the next catalytic cycle.
Alternatively, CO insertion to the hydropalladation intermediate
C followed by E-to-Z isomerization and intramolecular
aminolysis could also give the final product (path B).
In summary, we have successfully developed an efficient
palladium-catalyzed intramolecular hydroaminocarbonylation of
2-alkynyl benzylamines in the absence of acidic additive, which
allows for the synthesis of a wide range of biologically active
seven- and eight-membered lactams with high chemoselectivity
and regioselectivity under mild reaction conditions. The catalytic
system presents broad functional group tolerance and substrate
scope. More importantly, this novel strategy provides effective
access to medium-sized heterocycles and shows great potential in
synthetic chemistry. Further investigations aimed at gaining a
detailed mechanistic understanding of this reaction and
developing more synthetically useful transformations are
currently underway.
̀
I.; Ando, S.; Gabriele, B. Chem. - Eur. J. 2016, 22, 3053.
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B.; Li, L.; Zhu, X.-Q.; Yan, J.-Z.; Guo, Y.-L.; Ye, L.-W. Angew. Chem., Int.
Ed. 2017, 56, 4015.
(7) (a) Sammes, P. G. Chem. Rev. 1976, 76, 113. (b) Kametani, T.;
Nagahara, T. Heterocycles 1987, 25, 729. (c) Tsang, W. Y.; Ahmed, N.;
Hinchliffe, P. S.; Wood, J. M.; Harding, L. P.; Laws, A. P.; Page, M. I. J.
Am. Chem. Soc. 2005, 127, 17556. (d) Albrecht, S.; Defoin, A.; Salomon,
ASSOCIATED CONTENT
* Supporting Information
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E.; Tarnus, C.; Wetterholm, A.; Haeggstrom, J. Z. Bioorg. Med. Chem.
̈
S
2006, 14, 7241. (e) Billamboz, M.; Bailly, F.; Lion, C.; Touati, N.; Vezin,
The Supporting Information is available free of charge on the
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H.; Calmels, C.; Andreola, M.-L.; Christ, F.; Debyser, Z.; Cotelle, P. J.
Med. Chem. 2011, 54, 1812. (f) Yada, A.; Okajima, S.; Murakami, M. J.
Am. Chem. Soc. 2015, 137, 8708.
Experimental details and full spectroscopic data for all new
X-ray structure of 2a (CIF)
X-ray structure of 2c (CIF)
X-ray structure of 2e (CIF)
X-ray structure of 2j (CIF)
X-ray structure of 2k (CIF)
X-ray structure of 2l (CIF)
X-ray structure of 2q (CIF)
(8) For selected examples, see: (a) Tang, S.; Yu, Q.-F.; Peng, P.; Li, J.-
H.; Zhong, P.; Tang, R.-Y. Org. Lett. 2007, 9, 3413. (b) Park, J.; Kim, E.;
Chung, Y. Org. Lett. 2008, 10, 4719.
(9) Hu, Y.; Shen, Z.; Huang, H. ACS Catal. 2016, 6, 6785.
(10) CCDC 1561014 (2a), 1561015 (2c), 1561016 (2e), 1561017
(2j), 1561018 (2k), 1561019 (2l) and 1561022 (2q) contain the
supplementary crystallographic data for this paper. This data can be
obtained free of charge from the Cambridge Crystallographic Data
(11) Hickin, J. A.; Ahmed, A.; Fucke, K.; Ashcroft, M.; Jones, K. Chem.
Commun. 2014, 50, 1238.
(12) For reviews, see: (a) Wu, X.-F.; Neumann, H.; Beller, M. Chem.
Soc. Rev. 2011, 40, 4986. (b) Wu, X.-F.; Neumann, H.; Beller, M. Chem.
Rev. 2013, 113, 1. (c) Wu, X.-F.; Fang, X.; Wu, L.; Jackstell, R.;
Neumann, H.; Beller, M. Acc. Chem. Res. 2014, 47, 1041. For selected
examples, see: (d) Fang, X.; Jackstell, R.; Beller, M. Angew. Chem., Int. Ed.
2013, 52, 14089. (e) Liu, H.; Yan, N.; Dyson, P. J. Chem. Commun. 2014,
50, 7848. (f) Fang, X.; Li, H.; Jackstell, R.; Beller, M. J. Am. Chem. Soc.
2014, 136, 16039. (g) Zhang, G.; Gao, B.; Huang, H. Angew. Chem., Int.
Ed. 2015, 54, 7657. (h) Cheng, J.; Qi, X.; Li, M.; Chen, P.; Liu, G. J. Am.
Chem. Soc. 2015, 137, 2480. (i) Sha, F.; Alper, H. ACS Catal. 2017, 7,
2220.
(13) For the selected examples of E−Z isomerization of alkenyl-Pd
species, see: (a) Chernyak, N.; Gorelsky, S. I.; Gevorgyan, V. Angew.
Chem., Int. Ed. 2011, 50, 2342. (b) Le, C. M.; Hou, X.; Sperger, T.;
Schoenebeck, F.; Lautens, M. Angew. Chem., Int. Ed. 2015, 54, 15897.
(c) Le, C. M.; Menzies, P. J. C.; Petrone, D. A.; Lautens, M. Angew.
Chem., Int. Ed. 2015, 54, 254. (d) Petrone, D. A.; Franzoni, I.; Ye, J.;
Rodríguez, J. F.; Poblador-Bahamonde, A. I.; Lautens, M. J. Am. Chem.
Soc. 2017, 139, 3546.
AUTHOR INFORMATION
■
Corresponding Author
ORCID
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This research was supported by the CAS Interdisciplinary
Innovation Team an the National Natural Science Foundation of
China (21672199).
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