Organic Letters
Letter
(d) Kawahara, R.; Fujita, K.; Yamaguchi, R. Angew. Chem., Int. Ed.
2012, 51, 12790. (e) Tseng, K. T.; Kampf, J. W.; Szymczak, N. K.
Organometallics 2013, 32, 2046. (f) Zeng, G.; Sakaki, S.; Fujita, K.;
Sano, H.; Yamaguchi, R. ACS Catal. 2014, 4, 1010. (g) Song, H.; Kang,
B.; Hong, S. ACS Catal. 2014, 4, 2889. (h) Chakraborty, S.; Lagaditis,
P. O.; Forster, M.; Bielinski, E. A.; Hazari, N.; Holthausen, M. C.;
Jones, W. D.; Schneider, S. ACS Catal. 2014, 4, 3994.
(10) For selected examples, see: (a) Yamaguchi, R.; Ikeda, C.;
Takahashi, T.; Fujita, K. J. Am. Chem. Soc. 2009, 131, 8410. (b) Wu, J.;
Talwar, D.; Johnston, S.; Yan, M.; Xiao, J. Angew. Chem., Int. Ed. 2013,
52, 6983. (c) Fujita, K.; Tanaka, Y.; Kobayashi, M.; Yamaguchi, R. J.
Am. Chem. Soc. 2014, 136, 4829. (d) Chakraborty, S.; Brennessel, W.
W.; Jones, W. D. J. Am. Chem. Soc. 2014, 136, 8564. (e) Talwar, D.;
Gonzalez-de-Castro, A.; Li, H.; Xiao, J. Angew. Chem., Int. Ed. 2015, 54,
5223.
In summary, we have demonstrated the first examples of
acceptorless dehydrogenative cyclization of o-aminobenzyl
alcohols with ketones to quinolines in water. Notably, this
research exhibits the potential for the construction of
heterocycles via acceptorless dehydrogenative reactions in
water catalyzed by water-soluble metal−ligand bifunctional
catalysts.
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
1
Experimental procedures, and H NMR and 13C NMR
(11) Kawahara, R.; Fujita, K.; Yamaguchi, R. J. Am. Chem. Soc. 2012,
134, 3643.
spectra of products (PDF)
(12) Qu, P.; Sun, C.; Ma, J.; Li, F. Adv. Synth. Catal. 2014, 356, 447.
(13) (a) Li, F.; Shan, H.; Chen, L.; Kang, Q.; Zou, P. Chem. Commun.
2012, 48, 603. (b) Li, F.; Sun, C.; Shan, H.; Zou, X.; Xie, J.
ChemCatChem 2013, 5, 1543. (c) Li, F.; Qu, P.; Ma, J.; Zou, X.; Sun,
C. ChemCatChem 2013, 5, 2178. (d) Sun, C.; Zou, X.; Li, F. Chem. -
Eur. J. 2013, 19, 14030. (e) Li, F.; Sun, C.; Wang, N. J. Org. Chem.
2014, 79, 8031. (f) Li, F.; Ma, J.; Wang, N. J. Org. Chem. 2014, 79,
10447. (g) Wang, R.; Ma, J.; Li, F. J. Org. Chem. 2015, 80, 10769.
(h) Li, F.; Lu, L.; Ma, J. Org. Chem. Front. 2015, 2, 1589. (i) Lu, L.;
Ma, J.; Qu, P.; Li, F. Org. Lett. 2015, 17, 2350. (j) Zhao, W.; Liu, P.; Li,
F. ChemCatChem 2016, 8, 1523. (k) Li, F.; Lu, L.; Liu, P. Org. Lett.
2016, 18, 2580.
(14) The enhancement of yield is probably due to the fact that the
produced hydrogen gas was removed away from the reaction system
under air-open conditions compared to that with a sealed nitrogen
atmosphere, which facilitates the reaction process.
(15) (a) Himeda, Y.; Onozawa-Komatsuzaki, N.; Miyazawa, S.;
Sugihara, H.; Hirose, T.; Kasuga, K. Chem. - Eur. J. 2008, 14, 11076.
(b) Fujita, K.; Kawahara, R.; Aikawa, T.; Yamaguchi, R. Angew. Chem.,
Int. Ed. 2015, 54, 9057.
(16) Although a ß-H elimination mechanism has been widely
accepted, Wang and co-workers proposed another possible mechanism
for the acceptorless dehydrogenation catalyzed by various catalysts
based on DFT computational studies: dehydrogenation via the metal−
ligand bifunctional active site takes place more favorably than ß-H
elimination, see: (a) Li, H.; Lu, G.; Jiang, J.; Huang, F.; Wang, Z. X.
Organometallics 2011, 30, 2349. (b) Li, H.; Jiang, J.; Lu, G.; Huang, F.;
Wang, Z. X. Organometallics 2011, 30, 3131. (c) Li, H.; Wang, X.;
Huang, F.; Lu, G.; Jiang, J.; Wang, Z. X. Organometallics 2011, 30,
5233. (d) Qu, S.; Dang, Y.; Song, C.; Wen, M.; Huang, K. W.; Wang,
Z. X. J. Am. Chem. Soc. 2014, 136, 4974.
AUTHOR INFORMATION
Corresponding Author
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
Financial support by the National Natural Science Foundation
of China (21272115) and the State Key Laboratory of Fine
Chemicals (KF1401) is greatly appreciated.
REFERENCES
■
(1) (a) Michael, J. P. Nat. Prod. Rep. 1997, 14, 605. (b) Michael, J. P.
Nat. Prod. Rep. 2002, 19, 742.
(2) (a) Becherer, J. D.; Boros, E. E.; Carpenter, T. Y.; Cowan, D. J.;
Deaton, D. N.; Haffner, C. D.; Jeune, M. R.; Kaldor, I. W.; Poole, J. C.;
Preugschat, F.; Rheault, T. R.; Schulte, C. A.; Shearer, B. G.; Shearer,
T. W.; Shewchuk, L. M.; Smalley, T. L.; Stewart, E. L.; Stuart, J. D.;
Ulrich, J. C. J. Med. Chem. 2015, 58, 7021. (b) Olson, M. E.; Abate-
Pella, D.; Perkins, A. L.; Li, M.; Carpenter, M. A.; Rathore, A.; Harris,
R. S.; Harki, D. A. J. Med. Chem. 2015, 58, 7419. (c) Wang, Z.; Wang,
Y.; Wang, B.; Li, W.; Huang, L.; Li, X. J. Med. Chem. 2015, 58, 8616.
(d) Brouwer, C.; Jenko, K.; Zoghbi, S. S.; Innis, R. B.; Pike, V. W. J.
Med. Chem. 2014, 57, 6240.
(3) Jones, G. In Comprehensive Heterocyclic Chemistry; Katritzky, A.
R., Rees, C. W., Eds.; Pergamon: New York, 1984; Vol. 2, p 395.
(4) For a selected review, see: Marco-Contelles, J.; Perez-Mayoral, E.;
Samadi, A.; Carreiras, M. C.; Soriano, E. Chem. Rev. 2009, 109, 2652.
(5) (a) Cho, C. S.; Kim, B. T.; Kim, T. J.; Shim, S. C. Chem. Commun.
2001, 2576. (b) Cho, C. S.; Kim, B. T.; Choi, H. J.; Kim, T. J.; Shim, S.
C. Tetrahedron 2003, 59, 7997. (c) Motokura, K.; Mizugaki, T.;
Ebitani, K.; Kaneda, K. Tetrahedron Lett. 2004, 45, 6029. (d) Martinez,
R.; Brand, G. J.; Ramon, D. J.; Yus, M. Tetrahedron Lett. 2005, 46,
3683. (e) Martinez, R.; Ramon, D. J.; Yus, M. Eur. J. Org. Chem. 2007,
2007, 1599. (f) Mierde, H. V.; Voort, P. V. D.; Vos, D. D.; Verpoort, F.
Eur. J. Org. Chem. 2008, 1625.
(17) Kawahara and co-workers have confirmed the ligand-promoted
dehydrogenation of alcohols with the liberation of hydrogen gas, see
ref 11.
(18) We have confirmed the ligand-promoted transfer hydrogenation
of the CC bond of an α,β-unsaturated ketone with an alcohol as the
hydrogen catalyzed by [Cp*Ir(2,2′-bpyO)(H2O)], see ref 13f.
(19) Fujita and co-workers have demonstrated the dehydrogenation
of C−C and C−N bonds of N-heterocycles catalyzed by iridium
complexes bearing a functional bipyridonate ligand, see: Fujita, K.;
Tanaka, Y.; Kobayashi, M.; Yamaguchi, R. J. Am. Chem. Soc. 2014, 136,
4829.
(6) (a) Cho, C. S.; Ren, W. X. J. Organomet. Chem. 2007, 692, 4182.
(b) Chen, B. W. J.; Chng, L. L.; Yang, J.; Wei, Y.; Yang, J.; Ying, J. Y.
ChemCatChem 2013, 5, 277.
(7) Taguchi, K.; Sakaguchi, S.; Ishii, Y. Tetrahedron Lett. 2005, 46,
4539.
(20) For support of the proposed mechanisms, the liberation of
hydrogen gas in the process of the cyclization of 1a with 2a was
(8) (a) Cho, C. S.; Ren, W. X.; Shim, S. C. Tetrahedron Lett. 2006,
47, 6781. (b) Cho, C. S.; Ren, W. X.; Yoon, N. S. J. Mol. Catal. A:
Chem. 2009, 299, 117.
(9) For selected examples, see: (a) Fujita, K.; Tanino, N.; Yamaguchi,
R. Org. Lett. 2007, 9, 109. (b) Fujita, K.; Yoshida, T.; Imori, Y.;
Yamaguchi, R. Org. Lett. 2011, 13, 2278. (c) Musa, S.; Shaposhnikov,
I.; Cohen, S.; Gelman, D. Angew. Chem., Int. Ed. 2011, 50, 3533.
D
Org. Lett. XXXX, XXX, XXX−XXX