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LETTER
see: Legault, C. Y.; Charette, A. B. J. Am. Chem. Soc. 2005,
127, 8966. (f) For isoquinolines, see: Lu, S. M.; Wang, Y.
Q.; Han, X. W.; Zhou, Y.-G. Angew. Chem. Int. Ed. 2006,
45, 2260. For quinoxalines, see: (g) Tang, W.-J.; Xu, L.-J.;
Fan, Q.-H.; Wang, J.; Fan, B.-M.; Lam, K.-H.; Chan, A. S.
C. Angew. Chem. Int. Ed. 2009, 48, 9135. (h) Mršić, N.;
Jerphagnon, T.; Minnaard, A. J.; Feringa, B. L.; de Vries,
J. G. Adv. Synth. Catal. 2009, 351, 2549.
2-(aroylmethyl)quinolines, and the tandem ATH/AH
reductions of 2-(aroylmethyl)quinolines with excellent
stereoselectivity by using phosphine-free Ru-TsDPEN
complex as the catalyst.12 Further application of this cata-
lytic system in the asymmetric reduction of other het-
eroaromatics and prochiral imines is in progress.
(6) Carey, A. R. E.; Fukata, G.; O’Ferrall, R. A. M.; Murphy,
Supporting Information for this article is available online at
M. G. J. Chem. Soc., Perkin Trans. 2 1985, 1711.
(7) For metal complexes containing diamine ligands for
asymmetric hydrogenation, see: (a) Ito, M.; Hirakawa, M.;
Murata, K.; Ikariya, T. Organometallics 2001, 20, 379.
(b) Ohkuma, T.; Utsumi, N.; Tsutsumi, K.; Murata, K.;
Sandoval, C. A.; Noyori, R. J. Am. Chem. Soc. 2006, 128,
8724. (c) Ohkuma, T.; Tsutsumi, K.; Utsumi, N.; Arai, N.;
Noyori, R.; Murata, K. Org. Lett. 2007, 9, 255. (d) Li, C.;
Xiao, J. J. Am. Chem. Soc. 2008, 130, 13208. (e) Chen, f.;
Wang, T.-L.; He, Y.-M.; Ding, Z.-Y.; Li, Z.-W.; Xu, L.-J.;
Fan, Q.-H. Chem. Eur. J. 2011, 17, 1109.
Acknowledgment
Financial support from the National Natural Science Foundation of
China (No. 20973178), the National Basic Research Program of
China (973 program, No. 2010CB833300), the Ministry of Health
(No. 2009ZX09501-017), and the Chinese Academy of Sciences is
gratefully acknowledged.
(8) Wang, X.-B.; Wang, D.-W.; Lu, S.-M.; Yu, C.-B.; Zhou,
Y.-G. Tetrahedron: Asymmetry 2009, 20, 1040.
References and Notes
(9) (a) Noyori, R.; Hashiguchi, S. Acc. Chem. Res. 1997, 30, 97.
(b) Hashiguchi, S.; Fujii, A.; Takehara, J.; Ikariya, T.;
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(1) For recent reviews, see: (a) Glorius, F. Org. Biomol. Chem.
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1357. (c) Kuwano, R. Heterocycles 2008, 76, 909.
(2) Wang, W.-B.; Lu, S.-M.; Yang, P.-Y.; Han, X.-W.; Zhou,
Y.-G. J. Am. Chem. Soc. 2003, 125, 10536.
(3) For selected recent examples of asymmetric hydrogenation
of quinolines, see: (a) Lu, S.-M.; Han, X.-W.; Zhou, Y.-G.
Adv. Synth. Catal. 2004, 346, 909. (b) Wang, D.-W.; Wang,
X.-B.; Wang, D.-S.; Lu, S.-M.; Zhou, Y.-G.; Li, Y.-X.
J. Org. Chem. 2009, 74, 2780. (c) Wang, D.-S.; Zhou,
Y.-G. Tetrahedron Lett. 2010, 51, 3014. (d) Xu, L.-J.; Lam,
K. H.; Ji, J. X.; Fan, Q.-H.; Lo, W.-H.; Chan, A. S. C. Chem.
Commun. 2005, 1390. (e) Tang, W.-J.; Zhu, S.-F.; Xu, L.-J.;
Zhou, Q.-L.; Fan, Q.-H.; Zhou, H.-F.; Lam, K.; Chan, A. S.
C. Chem. Commun. 2007, 613. (f) Wang, Z. J.; Deng, G. J.;
Li, Y.; He, Y. M.; Tang, W. J.; Fan, Q. H. Org. Lett. 2007,
9, 1243. (g) Reetz, M.; Li, X. Chem. Commun. 2006, 2159.
(h) Mršić, N.; Lefort, L.; Boogers, J. A. F.; Minnaard, A. J.;
Feringa, B. L.; de Vries, J. G. Adv. Synth. Catal. 2008, 350,
1081. (i) Tadaoka, H.; Cartigny, D.; Nagano, T.; Gosavi, T.;
Ayad, T.; Genêt, J. P.; Ohshima, T.; Ratovelomanana-Vidal,
V.; Mashima, K. Chem. Eur. J. 2009, 15, 9990.
(4) (a) Zhou, H. F.; Li, Z. W.; Wang, Z. J.; Wang, T. L.; Xu, L.
J.; He, Y. M.; Fan, Q.-H.; Pan, J.; Gu, L. Q.; Chan, A. S. C.
Angew. Chem. Int. Ed. 2008, 47, 8464. (b) Wang, Z.-J.;
Zhou, H.-F.; Wang, T.-L.; He, Y.-M.; Fan, Q.-H. Green
Chem. 2009, 11, 767. (c) Li, Z.-W.; Wang, T.-L.; He,
Y.-M.; Wang, Z.-J.; Fan, Q.-H.; Pan, J.; Xu, L.-J. Org. Lett.
2008, 10, 5265.
(11) For transition-metal-catalyzed asymmetric transfer
hydrogenation of quinolines in acidic aqueous buffer
solution, see: Wang, C.; Li, C.; Wu, X.; Pettman, A.; Xiao,
J. Angew. Chem. Int. Ed. 2009, 48, 6524.
(12) Typical procedure for the Ru-catalyzed asymmetric
ATH/AH reactions: Into a 50 mL glass-lined stainless steel
reactor with a magnetic stirring bar was charged (R,R)-1b
(0.6 mg, 0.001 mmol), substrate 2a (24.7 mg, 0.1 mmol) and
degassed EtOH (1 mL) under a nitrogen atmosphere, and the
mixture was stirred at r.t. for 24 h. Then, to the reaction
mixture was added a solution of 1.0 M TfOH in EtOH (100
mL, 0.001 mmol, 1 mol% cf substrate) under a nitrogen
atmosphere. The autoclave was closed, and H2 was initially
introduced into the autoclave at a pressure of 50 atm, before
being reduced to 1 atm. After this procedure was repeated
three times, the autoclave was pressurized with H2 to 50 atm.
Subsequently, the mixture was stirred under this H2 pressure
at r.t. for another 12 h. After carefully releasing the
hydrogen, the mixture was concentrated to afford the crude
product. The conversion and diastereoselectivity were
determined by 1H NMR analysis of the crude product.
Further purification was performed with a silica gel column
(PE–CH2Cl2, 1:1) to give the pure product, (+)-1-phenyl-2-
(1,2,3,4-tetrahydroquinolin-2-yl)ethanol (4a). Isolated
yield: 94%; >95:5 dr; >99% ee; [a]D20 +67.9 (c 1.00, CHCl3);
1H NMR (300 MHz, CDCl3): d = 7.38–7.29 (m, 5 H), 7.00–
6.95 (m, 2 H), 6.67–6.62 (m, 1 H), 6.49 (d, J = 7.8 Hz, 1 H),
5.02 (t, J = 6.6 Hz, 1 H), 3.55–3.47 (m, 1 H), 2.88–2.69 (m,
2 H), 1.97–1.90 (m, 3 H), 1.88–1.81 (m, 1 H); 13C NMR (75
MHz, CDCl3): d = 143.34, 143.14, 128.30, 127.56, 126.61,
125.70, 124.69, 120.69, 116.73, 113.99, 71.07, 47.79, 43.67,
26.95, 25.15; HRMS (ESI): m/z [M + H]+ calcd for
C17H20NO: 254.15394; found: 254.15385.
(5) For selected examples of asymmetric hydrogenation of other
heteroaromatic compounds, see: For indoles and pyrroles:
(a) Kuwano, R.; Sato, K.; Kurokawa, T.; Karube, D.; Ito, Y.
J. Am. Chem. Soc. 2000, 122, 7614. (b) Wang, D.-S.; Chen,
Q.-A.; Li, W.; Yu, C.-B.; Zhou, Y.-G.; Zhang, X. J. Am.
Chem. Soc. 2010, 132, 8909. (c) Kuwano, R.; Kashiwabara,
M.; Ohsumi, M.; Kusano, H. J. Am. Chem. Soc. 2008, 130,
808. (d) For furans, see: Kaiser, S.; Smidt, S. P.; Pfaltz, A.
Angew. Chem. Int. Ed. 2006, 45, 5194. (e) For pyridines,
Synlett 2011, No. 7, 939–942 © Thieme Stuttgart · New York