N. Mizuno et al.
Acknowledgements
Experimental Section
This work was supported in part by the Global COE Program (Chemistry
Innovation through Cooperation of Science and Engineering) and
Grants-in-Aid for Scientific Researches from the Ministry of Education,
Culture, Sports, Science and Technology. We are grateful to Prof. Y.
Inada (PF, KEK) for his help with the XAFS measurements.
General: NMR spectra were recorded on a JEOL JNM-EX-270 instru-
ment. 1H and 13C NMR spectra were measured at 270 and 67.8 MHz, re-
spectively, in [D1]chloroform with tetramethylsilane (TMS) as an internal
standard. GC analyses were performed on a Shimadzu GC-17 A instru-
ment with a flame ionization detector (FID) equipped with a Rt b-
CDEXM capillary column (internal diameter=0.25 mm, length=30 m)
or a DB-WAX capillary column (internal diameter=0.25 mm, length=
30 m). HPLC analyses were performed on a Shimadzu LC-10A instru-
ment with a UV detector equipped with a Chiralcel-OD column (internal
diameter=46 mm, length=25 cm) using n-hexane/2-propanol (95:5 v/v)
as an eluent. Mass spectra were recorded on a Shimadzu GCMS-QP2010
instrument equipped with a TC-5HT capillary column (internal diame-
ter=0.25 mm, length=30 m). The ICP-AES analyses were performed
[1] a) R. A. Sheldon, H. van Bekkum, Fine Chemical through Heteroge-
neous Catalysis, Wiley, Weinheim, 2001; b) G. Centi, F. Cavani, F.
Trifiro, Selective Oxidation by Heterogeneous Catalysis, Kluwer, New
York, 2001; c) I. V. Kozhevnikov, NATO Science Series, II: Mathe-
matics, Physics and Chemistry, Kluwer, New York, 2003, pp. 351–
380; d) B. Warren, S. T. Oyama, Heterogeneous Hydrocarbon Oxida-
tion, ACS, Washington, D. C., 1996; e) A. Bhan, E. Iglesia, Acc.
with
a Shimadzu ICPS-8100 instrument. The ESR measurements
ACHTUNGTRENNUNG(X-band) were performed with a JEOL JES-RE-1X instrument at 103 K
under an Ar atmosphere. The XRD patterns were measured with a
Rigaku MultiFlex instrument by using CuKa radiation (40 kV-50 mA).
The X-ray absorption spectra were recorded at the NW10A beam line of
[2] K. Yamaguchi, T. Koike, M. Kotani, M. Matsushita, S. Shinachi, N.
[3] J. W. Kim, T. Koike, M. Kotani, K. Yamaguchi, N. Mizuno, Chem.
Eur. J., 2008, 14, 4104.
PF at KEK, Japan (proposal No. 2007G096). A SiACTHNUTRGENUG(N 311) single crystal was
used to obtain the monochromated X-ray beam. Two ion chambers filled
with Ar and Kr were used as I0 and I detectors, respectively. For EXAFS
analysis, the oscillation was first extracted from the EXAFS data by a
spline smoothing method. The Fourier transformation of the k3-weighted
EXAFS oscillation from k space to r space was performed over the range
3.0–16.5 ꢁÀ1 to obtain an RDF. For the curve-fitting analysis, the empiri-
N. Mizuno, Angew. Chem. 2003, 115, 1517; Angew. Chem. Int. Ed.
À
cal phase shift and amplitude functions for Ru O and Ru···Ru were ex-
[5] a) H. Fujiwara, Y. Ogasawara, K. Yamaguchi, N. Mizuno, Angew.
Fujiwara, Y. Ogasawara, M. Kotani, K. Yamaguchi, N. Mizuno,
[6] a) R. A. Sheldon, Chirotechnology, Industrial Synthesis of Optically
Active Compounds, Dekker, New York, 1993; b) C. H. Wang, G. M.
Whitesides, Enzymes in Synthetic Organic Chemistry, Elsevier, Am-
sterdam, 1994.
tracted from the data for RuO2 and Ru metal. The data were analyzed
by using REX2000 software (version 2.5, Rigaku). The XPS measure-
ments were carried out on a JEOL JPS-90 instrument by using mono-
chromated AlKa radiation (hn=1486.6 eV). The X-ray anode was run at
200 W and the voltage was kept at 10 kV. The pass energy was fixed at
10.0 eV to ensure sufficient resolution to determine peak positions accu-
rately. The binding energies were calibrated by using the Au 4f7/2 signal
at 84.0 eV.
[7] a) H. Meerwein, R. Schmidt, Justus Liebigs Ann. Chem. 1925, 444,
221; b) A. Verley, Bull. Soc. Chim. Fr. 1925. 37, 537; c) W. Ponndorf,
Angew. Chem. 1926, 39, 138; d) K. Nishida, M. Noda, Chirality 2002,
14, 759; e) J. F. de Graauw, J. A. Peters, H. van Bekkum, J. Huskens,
[8] a) B. A. Persson, A. L. E. Larsson, M. Le Ray, J.-E. Bꢃckvall, J. Am.
N. ll, J. S. M. Samec, N. Hermanns, J.-E. Bꢃckvall, Tetrahedron Lett.
2002, 43, 4699; c) O. Pꢅmies, J.-E. Bꢃckvall, J. Org. Chem. 2002, 67,
1999, 40, 6281; e) J. H. Choi, Y. H. Kim, S. H. Nam, S. T. Shin, M.-J.
2002, 41, 2373; f) M.-J. Kim, Y. Chung, Y. K. Choi, H. K. Lee, D.
kas, A. N. E. Weissfloch, A. T. Rappaport, L. A. Cuccia, J. Org.
Dijksman, J. M. Elzinga, Y.-X. Li, I. W. C. E. Arends, R. A. Sheldon,
Reagents: Reagents and substrates were obtained from Tokyo Kasei, Al-
drich, and Fluka (reagent grade) and used without further purification.
2-Propanol (Kanto), however, was carefully purified (degassed) before
use.[19] Anatase TiO2 (ST-01, 316 m2 gÀ1), anatase TiO2 (JRC-TIO-1,
73 m2 gÀ1), rutile TiO2 (SUPER-TITANIA G-2, 3.2 m2 gÀ1), and Al2O3
(KHS-24, BET surface area: 160 m2 gÀ1) were obtained from Ishihara
Sangyo Kaisya Ltd., the Catalysis Society of Japan, Showa Denko K. K.,
and Sumitomo Chemical respectively. RuHAP ([RuCl]2+ species on hy-
droxyapatite, 9.1 wt%) was purchased from Wako.
Preparation of Ru(OH)x: An aqueous solution of RuCl3 (8.3 mm) was ad-
justed to pH 13.2 by addition of an aqueous solution of NaOH (1m), and
the resulting solution was stirred at room temperature (ca. 293 K) for
24 h. The solid was then filtered off, washed with a large amount of
water, and dried in vacuo to afford Ru(OH)x in approximately 80% yield
(based on RuCl3).
Procedures for catalytic reactions: All operations were carried out in a
glove box under Ar for the hydrogen-transfer reactions. A typical proce-
dure is as follows: Ru(OH)x/TiO2(A) (Ru: 1 mol%), (R)-1-phenylethanol
(1 mmol), and toluene (3 mL) were successively placed into a pyrex vial.
A teflon-coated magnetic stirrer bar was added, and the reaction mixture
was vigorously stirred (800 rpm) at 353 K under 1 atm of argon. After
3 h, the catalyst and the product(s) were separated by filtration (or cen-
trifugation), and the solid mixture was washed with toluene. Then,
diphenyl (internal standard, 0.3 mmol) was added to the combined organ-
ic solution, and the solution was analyzed by GC on a chiral column. The
separated catalyst was washed with an aqueous solution of NaOH (1m)
and water, and then dried in vacuo before being recycled.
2008, 350, 113; b) S. Wuyts, J. Wahlen, P. A. Jacobs, D. E. De Vos,
11486
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2008, 14, 11480 – 11487