Organic & Biomolecular Chemistry
Page 4 of 5
4
Selected reviews on quinolines synthesis, see: (a) C.-C. Cheng and
S.-J. Yan, Org. React., 1982, 28, 37; (b) Quinolines. The Chemistry
produces the cyclization product.
To distinguish between these two mechanisms, some additional
experiments were performed. Reaction of aniline or ortho-
aminopyridine with 2a under the reaction conditions could not
give the imine product of type A as evidenced by TLC analysis of
the reaction mixture under UV irradiation, which may suggest
that amino-carbonyl condensation with 2a is not favorable under
the reaction conditions compared to direct retro-aldol of 2a.
However, the presence of the ortho-aldehyde group in 1 may
affect the amino-carbonyl condensation of 1 with 2a, and
therefore path i cannot be completely excluded. Further efforts to
isolate/characterize possible reaction intermediates (such as A, B,
6
6
7
0
5
0
Vol. 32, part 3, p1; (c) M. Balasubramani Da nO I a: n1 d0 . 1J 0. 3 G9 ./ C K6 eOa By 0, 1I 4n 52F
Comprehensive Heterocyclic Chemistry II; A. R. Katritzky, C. W.
Rees and E. F. V. Scriven, Eds.; Pergamon: New York, 1996; Vol. 5,
Chapter 5.06, pp 245-300; (d) V. V. Kouznetsov, L. Y. V. Mendez,
and C. M. M. Gomez, Curr. Org. Chem., 2005, 9, 141–161; (e) J.
5
0
5
Marco-Contelles, E. Pe ́r ez-Mayoral, A. Samadi, M. C. Carreiras, E.
Soriano, Chem. Rev., 2009, 109, 2652; (f) V. V. Kouznetsov,
Tetrahedron, 2009, 65, 2721; (g) J. Barluenga, F. Rodrıguez and F.
J. Fananas, Chem.-Asian J., 2009, 4, 1036.
TM-catalyzed examples of quinolines: (a) R. C. Larock and M.-Y.
Kuo, Tetrahedron Lett., 1991, 32, 569; (b) J. Horn, S. P. Marsden, A.
Nelson, D. House and G. G. Weingarten, Org. Lett., 2008, 10, 4117;
1
5
1
5
D and E in Scheme 3) were unfortunately unsuccessful.
Therefore, at the current stage path ii seems to be more favorable,
but path i cannot be completely excluded.
(c) N. T. Patil and V. S. Raut, J. Org. Chem., 2010, 75, 6961; (d) M.
T. Stone, Org. Lett., 2011, 13, 2326; (e) R. Yan, W. Liu, C. Pan, X.
Zhou, X. Li, X. Kang and G. Huang, Org. Lett., 2013, 15, 4876; (f)
B. Liu, H. Gao, Y. Yu, W. Wu, and H. Jiang, J. Org. Chem., 2013,
1
75
7
8, 10319; (g) S. Murru, B. McGough and R. S. Srivastava, Org.
3
Conclusions
Biomol. Chem., 2014, 12, 9133; (h) L. Xi, R. Zhang, L. Zhang, S.
Chen and X. Yu, Org. Biomol. Chem., 2015, 13, 3924; (i) L. Wang,
J. Ferguson and F. Zeng, Org. Biomol. Chem., 2015, 13, 11486; (j) J.
D. Neuhaus, S. M. Morrow, M. Brunavs and M. C. Willis, Org.
Lett., 2016, 18, 1562.
Quinolines involving C-H activations, see: (a) S. Kaur, M. Kumar
and V. Bhalla, Chem. Commun., 2015, 51, 16327; (b) X. Liu, X. Li,
H. Liu, Q. Guo, J. Lan, R. Wang and J. You, Org. Lett., 2015, 17,
In summary, a copper-catalyzed transfer aldol reaction of β-
hydroxyketones with ortho-aminobenzaldehydes or
8
8
9
9
0
5
0
5
nicotinaldehydes is reported which produces directly quinolines
and naphthyridines in high yields and excellent selectivity. This
method is believed to involve a key retro-aldol reaction of β-
hydroxyketones (or imines) to generate in-situ copper-enolate
regioselectively, which should account for the observed excellent
chemo- and regioselectivity of the final products. Further studies
are directed to the reaction mechanism and application of this
retro-aldol strategy for the construction of other heterocycles.
2
0
6
2
936; (c) S. P. Shukla, R, K. Tiwari and A. K. Verma, J. Org.
Chem., 2012, 77, 10382; (d) G. Song, X. Gong and X. Li, J. Org.
Chem., 2011, 76, 7583; (e) X. Ji, H. Huang, Y. Li, H. Chen, and H.
Jiang, Angew. Chem., Int. Ed., 2012, 51, 7292; (f) L. Kong, S. Yu, X.
Zhou and X. Li, Org. Lett., 2016, 18, 588.
K. Murakami, H. Ohmiya, H. Yorimitsu and K. Oshima, Tetrahedron
Lett., 2008, 49, 2388.
R. K. Sodhi, S. Paul, V. K. Gupta and R. Kant, Tetrahedron Lett.,
2
S.-L. Zhang and Z.-L. Yu, J. Org. Chem., 2016, 81, 57.
2
5
7
8
9
Acknowledgements
015, 56, 1944.
This work was supported by the National Natural Science
Foundation of China (Nos. 21472068, 21202062) and the Natural
Science Foundation of Jiangsu Province (No. BK2012108).
10 S.-L. Zhang and Z.-Q. Deng, Org. Biomol. Chem., 2016, 14, 7282.
1
1
(a) Y. Bao, N. Kumagai and M. Shibasaki, Chem. Sci., 2015, 6, 6124;
b) S. Tosaki, K. Hara, V. Gnanadesikan, H. Morimoto, S. Harada,
3
0
(
M. Sugita, N. Yamagiwa, S. Matsunaga and M. Shibasaki, J. Am.
Chem. Soc., 2006, 128, 11776; (c) K. Hara, S. Tosaki, V.
Gnanadesikan, H. Morimoto, S. Harada, M. Sugita, N. Yamagiwa, S.
Matsunaga and M. Shibasaki, Tetrahedron, 2009, 65, 5030.
(a) S. Cannizzaro, Justus Biebigs Ann. Chem., 1853, 88, 129; (b) T. A.
Geissman, Org. React., 1944, I, 94.
Notes and references
1
1
1
1
1
00
The Key Laboratory of Food Colloids and Biotechnology, Ministry of
Education, School of Chemical and Material Engineering, Jiangnan
University, Wuxi 214122, Jiangsu Proince, China. Fax: +86-510-
85917763; Tel: +86-510-85917763; E-mail: slzhang@jiangnan.edu.cn
1
2
3
4
4
5
5
5
0
5
0
5
05 13 The pKa values of acetophenone and acetone are 24.7 and 26.5 in
DMSO. Please refer to: F. G. Bordwell, Acc. Chem. Res., 1988, 21,
†
Electronic Supplementary Information (ESI) available: Experimental
details, characterization data and NMR spectra for all the products. See
DOI: 10.1039/b000000x/
4
56.
For reviews on C−C activation, see: (a) C.-H. Jun, Chem. Soc. Rev.,
004, 33, 610; (b) Y. J. Park, J.-W. Park and C.-H. Jun, Acc. Chem.
Res., 2008, 41, 222; (c) L. Jiao and Z.-X. Yu, J. Org. Chem., 2013,
1
4
2
1
Quinolines biological properties: (a) G. Roma, M. D. Braccio, G.
10
15
20
Grossi, F. Mattioli and M. Ghia, Eur. J. Med. Chem., 2000, 35, 1021;
7
8
8, 6842; (d) F. Chen, T. Wang and N. Jiao, Chem. Rev., 2014, 114,
613; (e) G. Dong, C−C bond activation. In Topics in Current
(
b) Y.-L. Chen, K.–C. Fang, J.-Y. Sheu, S.-L. Hsu and C.-C. Tzeng,
J. Med. Chem., 2001, 44, 2374; (c) J. P. Michael, Nat. Prod. Rep.,
001, 18, 543; (d) S. Andrews, S. J. Burgess, D. Skaalrud, J. X.
Chemistry, Springer-Verlag, Berlin, 2014; Vol. 346; (f) L. Souillart
and N. Cramer, Chem. Rev., 2015, 115, 9410; (g) I. Marek, A.
Masarwa, P.-O. Delaye and M. Leibeling, Angew. Chem., Int. Ed.,
2
Kelly and D. H. Peyton, J. Med. Chem., 2010, 53, 916; (e) S. M.
Prajapati, K. D. Patel, R. H. Vekariya, S. N. Panchal and H. D. Patel,
RSC Adv., 2014, 4, 24463.
2
015, 54, 414.
1
5
TLC analysis of the reaction mixture of reaction of ortho-
aminobenzaldehyde with 2a showed that very minor amount of new
points appeared soon in 5 mins and gradually disappeared as the
reaction continued, but they were unable to be separated or
characterized.
2
Naphthyridines properties: (a) W. W. Paudler and R. M. Sheets, In
Advances in Heterocyclic Chemistry; Academic Press: New York,
1983; Vol. XXXIII, pp 147-184; (b) P. A. Lowe, In Comprehensive
Heterocyclic Chemistry; A. J. Boulton and A. R. Katritzky, Eds.;
Pergamon Press: Oxford, U.K., 1984; Vol. II, Chapter 2.11, pp 581-
6
27; (c) V. P. Litvinov, Advances in the Chemistry of
Naphthyridines. In Advances in Heterocyclic Chemistry; A. R.
Katritzky, Ed.; Academic Press: New York, 2006; Vol. 91, pp 189-
3
00.
3
P. Friedländer, Ber. Dtsch. Chem. Ges., 1882, 15, 2572.
4
|
Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]