COMMUNICATIONS
Table 2. Hydrogenation of ketones by the racemic [RuCl2(dm-binap)]
complex through asymmetric activation/deactivation.
Synthesis, Vol. I and II (Ed.: I. Ojima), VCH, New York, 1993 and
2000; d) H. B. Kagan, Comprehensive Organic Chemistry, Vol. 8,
Pergamon, Oxford, 1992; e) Asymmetric Catalysis (Ed.: B. Bosnich),
Martinus Nijhoff Publishers, Dordrecht, 1986.
[RuCl2((±)-dm-binap)(dmf)n ] (1) (0.4 mol%)
(R)-DM-DABN (2) (0.22 mol%)
[2] a) N. W. Alcock, J. M. Brown, P. J. Maddox, J. Chem. Soc. Chem.
Commun. 1986, 1532 ± 1534; b) J. M. Brown, P. J. Maddox, Chirality
1991, 3, 345 ± 354; c) K. Maruoka, H. Yamamoto, J. Am. Chem. Soc.
1989, 111, 789 ± 790; d) J. W. Faller, J. Parr, J. Am. Chem. Soc. 1993,
115, 804 ± 805; e) J. W. Faller, M. Tokunaga, Tetrahedron Lett. 1993, 34,
7359 ± 7362; f) J. W. Faller, D. W. I. Sams, X. Liu, J. Am. Chem. Soc.
1996, 118, 1217 ± 1218; g) R. Sablong, J. A. Osborn, J. W. Faller, J.
Organomet. Chem. 1997, 527, 65 ± 70.
[3] a) S. Matsukawa, K. Mikami, Enantiomer 1996, 1, 69 ± 73; b) K.
Mikami, S. Matsukawa, Nature 1997, 385, 613 ± 615; c) S. Matsukawa,
K. Mikami, Tetrahedron: Asymmetry 1997, 8, 815 ± 816; d) T. Ohkuma,
H. Doucet, T. Pham, K. Mikami, T. Korenaga, M. Terada, R. Noyori, J.
Am. Chem. Soc. 1998, 120, 1086 ± 1087; e) 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.
[4] M. Kitamura, M. Tokunaga, T. Ohkuma, R. Noyori, Org. Synth. 1993,
71, 1 ± 13.
[5] DM-DABN was named after 1,1'-binaphthyl-2,2'-diamine (DABN):
K. J. Brown, M. S. Berry, J. R. Murdoch, J. Org. Chem. 1985, 50, 4345 ±
4349.
[6] The single crystal was grown from a dichloromethane/diethyl ether/
hexane mixed solvent at room temperature. X-ray crystallographic
analysis was performed with a Bruker SMART 1000 diffractometer
(graphite monochromator, MoKa radiation, l 0.71073 ). Crystal
data for [RuCl2((R)-dm-dabn)((R)-binap)]: C66H52Cl2N2P2Ru, red-
dish-orange, crystal dimensions 0.07 Â 0.17 Â 0.22 mm, orthorhombic,
space group P21212 (No. 18), a 20.822(3), b 22.130(3), c
O
OH
*
dpen (3) (0.2 mol%)
+ H2
Ar
Ar
KOH (0.8 mol%)
2-propanol
RT
8 atm
ketones
O
O
7: R = H
O
O
8a: R = o-Me
8b: R = m-Me
8c: R = p-Me
R
4
6
9
Ketones
(R)-2[a]
3
Time [h]
ee [%]
Yield [%]
4
4
6
6
7
7
±
(S,S)
(S,S)
(S,S)
(S,S)
(S,S)
(S,S)
(S,S)
(S,S)
(S,S)
(S,S)
(S,S)
(S,S)
(R,R)
(R,R)
4
4
4
4
4
4
4
4
6
4
4
4
4
4
96 (R)
80 (R)
91 (R)
45 (R)
95 (R)
70 (R)
95 (R)
82 (R)
95 (R)
60 (R)
93 (R)
60 (R)
92 (R)
84 (R)
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99
> 99[b]
> 99[b]
±
±
8a
8a
8b
8b
8c
8c
9
±
±
±
±
13.1320(18) , V 6051.2(14) 3, Z 4, 1calcd 1.215 gcmÀ3
,
9
m(MoKa) 1.43 cmÀ1, T 103 K, 10304 reflections were independent
and unique, and 6256 with I > 2s(I) (2qmax 24.78) were used. The
structure was solved by direct methods and expanded using Fourier
techniques. The non-hydrogen atoms were refined anisotropically.
Hydrogen atoms were included but not refined. R 0.095, wR2
0.2116. Crystallographic data (excluding structure factors) for the
structure reported inthis paper have beendeposited with the
Cambridge Crystallographic Data Centre as supplementary publica-
tionno. CCDC-144099. Copies of the data canbe obtained free of
charge onapplicationto CCDC, 12 UinonRoad, Cambridge
CB21EZ, UK (fax: (44)1223-336-033; e-mail: deposit@ccdc.cam.
ac.uk).
[a] denotes the presence of (R)-2. [b] Racemic [RuCl2(Tol-binap)]
was used; Tol-BINAP (2,2'-bis(di-4-tolylphosphanyl)-1,1'-binaphthyl).
stream of argon. After the mixture had been stirred at room temperature
for 30 min, the dichloromethane was removed under reduced pressure. The
autoclave was againpurged with argonafter the additionof ( S,S)-DPEN
(3; 1.0 mg, 4.5 mmol). 2-Propanol (2.8 mL) was added to the autoclave
under a stream of argon, followed by the addition of KOH/2-propanol
(0.5m, 40 mL, 20 mmol) with stirring at room temperature for 30 min.
1'-Acetonaphthone (4; 0.38 mL , 2.5 mmol) was added to the autoclave at
room temperature under a stream of argon, and then hydrogen was
introduced at a pressure of 8 atm. After vigorously stirring the mixture for
4 h at room temperature, the solvent was removed under reduced pressure.
The residue was filtered through a short columnof silica gel. The chemical
yield and enantiomeric ratio of 1-(1-naphthyl)ethanol (5) were calculated
by gas chromatography ona columnwith a chiral stationary phase ( >99%,
96% ee (R)). The product could also be isolated by columnchromatog-
raphy onsilica gel (eluent, hexane/EtOAc 5/1) to give 426 mg (99%) of 5.
[a]2D8 75.5 (c 1.0, CHCl3) (Ref. [12] [a]D25 78.9 (c 1, CHCl3), R
isomer); 1H NMR (300 MHz, CDCl3): d 1.59 (d, J 6.6 Hz, 3H, CH3),
1.90 (d, J 3.6 Hz, 1H, OH), 5.59 (dq, J 3.6, 6.6 Hz, 1H, CH), 7.37 ± 7.51
(m, 3H, aromatic CH), 7.60 (d, J 6.6 Hz, 1H, aromatic CH), 7.70 (d, J
8.1 Hz, 1H, aromatic CH), 7.78 ± 7.81 (m, 1H, aromatic CH), 8.02 ± 8.05 (m,
[7] a) P. Mangeney, T. Tejero, A. Alexakis, F. Grosjean, J. Normant,
Synthesis 1988, 255 ± 257; b) S. Pikul, E. J. Corey, Org. Synth. 1993, 71,
22 ± 29.
[8] The 1H NMR spectrum of the mixture of [RuCl2((S,S)-dpen)((S)-
binap)] and [RuCl2((R)-dm-dabn)((R)-binap)] shows: d 2.92 (m,
2H, NH2 of DPEN), 3.19 (m, 2H, NH2 of DPEN), 3.80 (d, J 9.6 Hz,
2H, NH2 of DM-DABN), 4.20 (m, 2H, CH-NH2 of DPEN), 4.69 (d,
J 9.6 Hz, 2H, NH2 of DM-DABN).
[9] For the hydrogenation of ketones by [RuCl2(dpen)(binap)], see: a) T.
Ohkuma, H. Ooka, S. Hashiguchi, T. Ikariya, R. Noyori, J. Am. Chem.
Soc. 1995, 117, 2675 ± 2676; b) T. Ohkuma, H. Ooka, T. Ikariya, R.
Noyori, J. Am. Chem. Soc. 1995, 117, 10417 ± 10418; c) T. Ohkuma, H.
Ooka, M. Yamakawa, T. Ikariya, R. Noyori, J. Org. Chem. 1996, 61,
4872 ± 4873; d) T. Ohkuma, H. Ikehira, T. Ikariya, R. Noyori, Synlett
1997, 467 ± 468; e) H. Doucet, T. Ohkuma, K. Murata, T. Yokozawa,
M. Kozawa, E. Katayama, A. F. England, T. Ikariya, R. Noyori,
Angew. Chem. 1998, 110, 1792 ± 1796; Angew. Chem. Int. Ed. 1998, 37,
1703 ± 1707; f) 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.
1H, aromatic CH); GC (columnCP-Cyclodextr-in
b-2,3,6-M-19,
i.d. 0.25 mm  25 m, CHROMPACK; carrier gas, nitrogen (75 KPa);
columntemp. 160 8C; injection temp. 1908C; split ratio 100/1), retention
time (tR); (R)-()-5: 32.7 min(98.1%), ( S)-(À)-5: 31.6 min(1.9%), 4:
21.3 min(0%).
[10] For the six-membered cyclic transition state, see: a) M. Yamakawa, H.
Ito, R. Noyori, J. Am. Chem. Soc. 2000, 122, 1466 ± 1478; b) K. Murata,
T. Ikariya, J. Org. Chem. 1999, 64, 2186 ± 2187; c) K.-J. Haack, S.
Hashiguchi, A. Fujii, T. Ikariya, R. Noyori, Angew. Chem. 1997, 109,
297 ± 300; Angew. Chem. Int. Ed. Engl. 1997, 36, 285 ± 288; d) R.
Noyori, S. Hashiguchi, Acc. Chem. Res. 1997, 30, 97 ± 102; for the
dihydridoruthenium species, see: e) A. Aranyos, G. Csjernyik, K. J.
Received: April 13, 2000 [Z14986]
[1] a) R. Noyori, Asymmetric Catalysis in Organic Synthesis, Wiley, New
York, 1994; b) H. Brunner, W. Zettlmeier, Handbook of Enantiose-
lective Catalysis, VCH, Weinheim, 1993; c) Catalytic Asymmetric
Â
Szabo, J.-E. Bäckvall, Chem. Commun. 1999, 351 ± 352, and references
Angew. Chem. Int. Ed. 2000, 39, No. 20
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