H. Yamamoto, Springs, Berlin, vol. 1, ch. 6, 1999, pp. 199–246;
(c) T. Ohkuma, M. Kitamura and R. Noyori, in Catalytic
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2000, ch. 1, pp. 1–110; (d) W. Tang and X. Zhang, Chem. Rev.,
2003, 103, 3029.
2 (a) R. Noyori and T. Ohkuma, Angew. Chem., Int. Ed., 2001, 40,
40; (b) R. Noyori, Adv. Synth. Catal., 2003, 345, 15; (c) R. Noyori
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and M. Wills, Tetrahedron: Asymmetry, 1999, 10, 2045;
(e) S. Gladiali and E. Alberico, Chem. Soc. Rev., 2006, 35, 226;
(f) T. Ikariya and A. J. Blacker, Acc. Chem. Res., 2007, 40, 1300.
3 (a) S. Hashiguchi, A. Fujii, J. Takehara, T. Ikariya and R. Noyori,
J. Am. Chem. Soc., 1995, 117, 7562; (b) J.-X. Gao, T. Ikariya and
R. Noyori, Organometallics, 1996, 15, 1087; (c) A. Fujii,
S. Hashiguchi, N. Uematsu, T. Ikariya and R. Noyori, J. Am.
Chem. Soc., 1996, 118, 2521; (d) K.-J. Haack, S. Hashiguchi,
A. Fujii, T. Ikariya and R. Noyori, Angew. Chem., Int. Ed. Engl.,
1997, 36, 285.
Fig. 2 Proposed transition state of the six-membered pericyclic ring.
Table 2 Asymmetric hydrogenation of ketones 3 by Ru-indan–amboxa
4 (a) X. Li, X. Wu, W. Chen, F. E. Hancock, F. King and J. Xiao,
Org. Lett., 2004, 6, 3321; (b) X. Wu, X. Li, F. King and J. Xiao,
Angew. Chem., Int. Ed., 2005, 44, 3407; (c) D. S. Matharu,
J. E. D. Martins and M. Wills, Chem.–Asian J., 2008, 3, 1374;
(d) F. K. Cheung, A. M. Hayes, J. Hannedouche, A. S. Y. Yim and
M. Wills, J. Org. Chem., 2005, 70, 3188.
Entry
R
R1
Conv.b (%)
Eec (%)
5 (a) P. Maire, T. Buttner, F. Breher, P. L. Floch and
¨
(b) T. Zweifel, J.-V. Naubron, T. Buttner, T. Ott and
¨
H. Grutzmacher, Angew. Chem., Int. Ed., 2005, 44, 6318;
¨
H. Grutzmacher, Angew. Chem., Int. Ed., 2008, 47, 3245.
1
C6H5
C6H5
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Et
iPr
>99
97
>99
>99
82
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
95
95 (R)
95 (R)
97 (R)
92 (R)
93 (R)
95 (R)
81 (R)
90 (R)
93 (R)
80 (R)
83 (R)
92 (R)
94 (R)
87 (R)
93 (R)
91 (R)
92 (R)
95 (R)
42 (R)
65 (R)
2d
3
o-MeC6H4
o-ClC6H4
o-MeOC6H4
m-MeC6H4
m-ClC6H4
m-MeOC6H4
p-MeC6H4
p-ClC6H4
p-FC6H4
p-MeOC6H4
1-Naphthyl
2-Naphthyl
C6H5
¨
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
6 (a) H. Doucet, T. Ohkuma, K. Murata, T. Yokozawa, M. Kozawa,
E. Katayama, A. F. England, T. Ikariya and R. Noyori, Angew.
Chem., Int. Ed., 1998, 37, 1703; (b) T. Ohkuma, M. Koizumi,
K. Muniz, G. Hilt, C. Kabuto and R. Noyori, J. Am. Chem. Soc.,
2002, 124, 6508; (c) C. A. Sandoval, T. Ohkuma, K. Muniz and
R. Noyori, J. Am. Chem. Soc., 2003, 125, 13490.
7 M. J. Burk, W. Hems, D. Herzberg, C. Malan and A. Zanotti-
Gerosa, Org. Lett., 2000, 2, 4173.
8 (a) J. Wu, H. Chen, W.-H. Kwok, R.-W. Guo, Z.-Y. Zhou,
C.-H. Yeung and A. S. C. Chan, J. Org. Chem., 2002, 67, 7908;
(b) J. Wu, J.-X. Ji, R.-W. Guo, C.-H. Yeung and A. S. C. Chan,
Chem.–Eur. J., 2003, 9, 2963.
9 J.-H. Xie, L.-X. Wang, Y. Fu, S.-F. Zhu, B.-M. Fan, H.-F. Duan
and Q.-L. Zhou, J. Am. Chem. Soc., 2003, 125, 4404.
10 W. Li, X. Sun, L. Zhou, G. Hou, S. Yu and X. Zhang, J. Org.
Chem., 2009, 74, 1397.
11 Y. Jiang, Q. Jiang and X. Zhang, J. Am. Chem. Soc., 1998, 120, 3817.
12 R. Noyori, M. Yamakawa and S. Hashiguchi, J. Org. Chem., 2001,
66, 7931.
C6H5
C6H5
Cyclopropyl
Me
Me
80
Cyclohexyl
tBu
>99
45
>99
iPr
Me
a
The reactions were carried out with 0.4 mmol of substrate in 2 mL of
solvent in the presence of 1 mol% of Ru catalyst at r.t. for 15 h unless
13 Q. Jiang, Y. Jiang, D. Xiao, P. Cao and X. Zhang, Angew. Chem.,
Int. Ed., 1998, 37, 1100.
b
otherwise specified. Substrate/base = 20. The conversions were
c
determined by GC. The enantiomeric excesses (configuration
14 T. Ohkuma, C. S. Sandoval, R. Srinivasan, Q. Lin, Y. Wei,
K. Muniz and R. Noyori, J. Am. Chem. Soc., 2005, 127, 8288.
15 For the application of cis-aminoindanol in asymmetric synthesis
and catalysis, see: (a) E. Didier, B. Loubinoux, G. M. Ramos
Tombo and G. Rihs, Tetrahedron, 1991, 47, 4941; (b) A. K. Ghosh,
S. Fidanze and C. H. Senanayake, Synthesis, 1998, 937;
(c) N. J. Gilmore, S. Jones and M. P. Muldowney, Org. Lett.,
2004, 6, 2805; (d) M. Bandini, P. G. Cozzi, L. Negro and
A. Umani-Ronchi, Chem. Commun., 1999, 39; (e) I. Gallou and
H. Senanayake, Chem. Rev., 2006, 106, 2843; (f) C. H. Senanayake,
D. Krishnamurthy and I. Gallou, in Handbook of Chiral Chemicals,
ed. D. Ager, CRC, Boca Raton, FL, 2nd edn, 2006, pp. 319–343.
16 (a) M. Ito and T. Ikariya, Chem. Commun., 2007, 5134; (b) M. Ito,
A. Sakaguchi, C. Kobayashi and T. Ikariya, J. Am. Chem. Soc.,
2007, 129, 290; (c) M. Ito, A. Osaku, C. Kobayashi, A. Shiibashi
and T. Ikariya, Organometallics, 2009, 28, 390.
d
indicated in parentheses) were determined by chiral GC. 0.1%
Catalyst loading.
aryl alkyl and aliphatic ketones. The tunable nature of this
ligand leaves a great potential for broadening the ketone
substrate scope, especially for pure aliphatic ketones. Further
investigation of ambox ligand system and its application in
other asymmetric reactions will be reported in due course.
We are grateful for the financial support from the National
Institutes of Health (GM58832) and Merck & Co., Inc., for
financial support.
17 T. Ohkuma, N. Utsumi, K. Tsutsumi, K. Murata, C. Sandoval and
R. Noyori, J. Am. Chem. Soc., 2006, 128, 8724.
Notes and references
1 (a) R. Noyori, Asymmetric Catalysis in Organic Synthesis, Wiley,
New York, 1994; (b) T. Ohkuma and R. Noyori, in Comprehensive
Asymmetric Catalysis, ed. E. N. Jacobsen, A. Pfaltz,
18 Similar studies of the N-substituting effect on the performance of
Ru-Ph–ambox in transfer hydrogenation were carried out in
ref. 11.
ꢀc
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Chem. Commun., 2010, 46, 3979–3981 | 3981