Ru(II)-CatalyzedAsymmetric Hydrogenation of Ketones
COMMUNICATIONS
room temperature for 10 hours, the reaction was stopped. The
solvent was removed under reduced pressure and the residue
was submittedto 1H NMR analysis to assess the conversion
of the starting materials. The enantiomeric excess of the prod-
uct was determined by chiral GC or HPLC.
40, 40–73; d) W. Tang, X. Zhang, Chem. Rev. 2003, 103,
3029–3070.
[2] For leading references, see: a) T. Ohkuma, H. Ooka, T.
Ikariya, R. Noyori, J. Am. Chem. Soc. 1995, 117, 10417–
10418; b) T. Ohkuma, H. Ooka, S. Hashiguchi, T. Ikariya,
R. Noyori, J. Am. Chem. Soc. 1995, 117, 2675–2676; c) H.
Doucet, T. Ohkuma, K. Murata, T. Yokozawa, M. Koza-
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Ed. 1998, 37, 1703–1707; d) T. Ohkuma, M. Koizumi, H.
Doucet, T. Pham, M. Kozawa, K. Murata, E. Katayama,
T. Yokozawa, T. Ikariya, R. Noyori, J. Am. Chem. Soc.
1998, 120, 13529–13530; e) T. Ohkuma, D. Ishii, H. Tak-
eno, R. Noyori, J. Am. Chem. Soc. 2000, 122, 6510–
Crystal Data for RuCl2(P1)2(R,R)-DPEN
C50H46N2Cl2P2Ru, Mr ¼908.80, orthorhombic, space group
P212121, a¼13.0457(7), b¼16.5901(10), c¼20.0597(12) ;
V¼4341.5(4) 3, Z¼4, 1calc ¼1.390 g·cmꢀ3, Mo-Ka radiation
(l¼0.71073 ), crystal dimensions 0.752ꢁ0.653ꢁ0.608 mm3.
A total of 26,682 reflections were collectedon a Bruker Smart
CCD area detector at 293(2)K, of which 10027 were independ-
ent and8,908 were greater than 2 s(I). The structure was solved
by direct methods and refined with using full-matrix least-
squares on F2 using the SHELXTL (version 6.10) software
˜
6511; f) T. Ohkuma, M. Koizumi, K. Muniz, G. Hilt, C.
Kabuto, R. Noyori, J. Am. Chem. Soc. 2002, 124, 6508–
6509.
package. Final residuals, R1¼0.0392, wR2¼0.0817 (all data),
[3] For the mechanism of asymmetric hydrogenation of ke-
ꢀ3
Pmax, Pmin ¼0.670, ꢀ0.617
.
tones catalyzedby [RuCl {BINAP}{diamine}] complexes,
2
see: a) C. A. Sandoval, T. Ohkuma, K. Kuniz, R. Noyori,
J. Am. Chem. Soc. 2003, 125, 13490–13503; b) R. Hart-
mann, P. Chan, Angew. Chem. 2001, 113, 3693–3697; An-
gew. Chem. Int. Ed. 2001, 40, 3581–3585; c) K. Abdur-Ra-
shid, M. Faatz, A. J. Lough, R. H. Morris, J. Am. Chem.
Soc. 2001, 123, 7473–7474.
Crystal Data for [RuCl2{P3}2{(R,R)-DPEN}]
C62H70N2Cl2P2Ru, Mr ¼1077.11, monoclinic, space group P21,
a¼19.4269(19), b¼12.9634(13), c¼23.563(2) , b¼
109.372(2)8, V¼5598.2(10) 3, Z¼4, 1calc ¼1.278 g·cmꢀ3
,
[4] a) T. Ohkuma, H. Doucet, T. Pham, K. Mikami, T. Kore-
naga, M. Terada, R. Noyori, J. Am. Chem. Soc. 1998,
120,1086–1087; b) K. Mikami, T. Korenaga, M. Terada,
T. Ohkuma, T. Pham, R. Noyori, Angew. Chem. 1999,
111, 517–519; Angew. Chem. Int. Ed. 1999, 38, 495–497;
c) K. Mikami, T. Korenaga, T. Ohkuma, R. Noyori, An-
gew. Chem. 2000, 112, 3854–3857; Angew. Chem. Int.
Ed. 2000, 39, 3707–3709.
[5] D. G. Genov, D. J. Ager, Angew. Chem. 2004, 116, 2876–
2879; Angew. Chem. Int. Ed. 2004, 43, 2816–2819.
[6] For reviews, see: a) K. Ding, H. Du, Y. Yuan, J. Long,
Chem. Eur. J. 2004, 10, 2872–2884; b) M. T. Reetz, Angew.
Chem. 2001, 113, 292–320; Angew. Chem. Int. Ed. 2001,
40, 284–310.
Mo-Ka radiation (l¼0.71073 ), crystal dimensions 0.495ꢁ
0.210ꢁ0.071 mm3. A total of 32,727 reflections were collected
on a Bruker Smart CCD area detector at 293(2)K, of which
21118 were independent and 7212 were greater than 2s(I).
The structure was solved by direct methods and refined with
full-matrix least-squares on F2 using the SHELXTL (version
6.10) software package. Final residuals, R1¼0.0666, wR2¼
ꢀ3
0.1435 (all data), Pmax, Pmin ¼0.892, ꢀ0.912
.
CCDC-260521 andCCDC-260522 contain the supplemen-
tary crystallographic data for this paper. These data can be ob-
ving.html (or from the Cambridge CB21EZ, UK; fax: (þ44)
1223-336-033; or e-mail: deposit@ccdec.cam.ac.uk).
[7] a) D. W. Robertson, J. H. Krushinski, R. W. Fuller, J. D.
Leander, J. Med. Chem. 1988, 31, 1412–1417; b) C. Suma-
lee, K. Mei-Ping, P. Chitchanum, P. Vichukorn, F. Cather-
ine, J. Med. Chem. 1992, 35, 4492–4497.
Acknowledgements
Financial support from the NSFC, CAS and the Major Basic Re-
search Development Program of China (Grant no.
G2000077506) and Ministry of Science and Technology of
Shanghai Municipality is gratefully acknowledged.
[8] For examples of analogous Noyori catalysts, see: a) P. Cao,
X. Zhang, J. Org. Chem. 1999, 64, 2127–2129; b) M. J.
Burk, W. Hems, D. Herzberg, C. Malan, A. Zanotti-Gero-
sa, Org. Lett. 2000, 2, 4173–4174; c) J. H. Xie, L. X. Wang,
Y. Fu, S. F. Zhu, B. M. Fan, H. F. Duan, Q. L. Zhou, J. Am.
Chem. Soc. 2003, 125, 4404–4405; d) J. Wu, J. X. Ji, R.
Guo, C.-H. Yeung, A. S. C. Chan, Chem. Eur. J. 2003, 9,
2963–2968; e) J. P. Henschke, A. Zanotti-Gerosa, P. Mor-
an, P. Harrison, B. Mullen, G. Casy, I. C. Lennon, Tetrahe-
dron Lett. 2003, 44, 4379–4383; f) A. Hu, H. L. Ngo, W.
Lin, Org. Lett. 2004, 6, 2937–2940; g) R. Guo, R. H. Mor-
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References and Notes
[1] a) Comprehensive Asymmetric Catalysis, (Ed s.: E. N. Ja-
cobsen, A. Pfaltz, H. Yamamoto), Springer, Berlin, 1999,
ꢀ
Vols. I III; b) Catalysis Asymmetric Synthesis, 2ndedn.,
(Ed.: I. Ojima), Wiley-VCH, New York, 2000; for compre-
hensive reviews, see: c) R. Noyori, T. Ohkuma, Angew.
Chem. 2001, 113, 40–75; Angew. Chem. Int. Ed. 2001,
Adv. Synth. Catal. 2005, 347, 1193–1197
asc.wiley-vch.de
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