Organometallics
Article
(bottom) using 2-PrOH as the eluent. The filtrate obtained was analyzed
by either GC or HPLC (for details see Supporting Information).
General Procedure for the Asymmetric Hydrogenation of
Ketones. For hydrogenations a customized Symyx high-throughput
screening system was used. All hydrogenations were carried out for
16 h at rt under hydrogen gas at a pressure of 25 bar and a substrate to
catalyst ratio of 25:1. Typically the following amounts of substrate,
catalyst, and solvent were used: 41.67 μmol of substrate and 1.67 μmol
of catalyst precursor in a total of 500 μL of solvent (for analysis data
see Supporting Information).
(6) (a) Naud, F.; Spindler, F.; Ruggeberg, C. J.; Schmidt, A. T.;
̈
Blaser, H. U. Org. Process Res. Dev. 2007, 11, 519−523. (b) Palmer, A.
M.; Nettekoven, U. Tetrahedron: Asymmetry 2007, 18, 2381−2385.
(7) (a) Schuecker, R.; Mereiter, K.; Spindler, F.; Weissensteiner, W.
Adv. Synth. Catal. 2010, 352, 1063−1074. (b) Espino, G.; Xiao, L.;
Puchberger, M.; Mereiter, K.; Spindler, F.; Manzano, B. R.; Jalon, F.
A.; Weissensteiner, W. Dalton Trans. 2009, 2751−2763. (c) Wang, Y.;
Weissensteiner, W.; Mereiter, K.; Spindler, F. Helv. Chim. Acta 2006,
89, 1772−1782. (d) Sturm, T.; Weissensteiner, W.; Spindler, F. Adv.
Synth. Catal. 2003, 345, 160−164.
(8) Schuecker, R.; Zirakzadeh, A.; Mereiter, K.; Spindler, F.;
Weissensteiner, W. Organometallics 2011, 30, 4711−4719.
(9) (a) Bertogg, A.; Togni, A. Organometallics 2006, 25, 622−630.
(b) Cabou, J.; Brocard, J.; Pelinski, L. Tetrahedron Lett. 2005, 46,
1185−1188.
ASSOCIATED CONTENT
■
S
* Supporting Information
Text giving full experimental descriptions and spectroscopic
data for all newly synthesized ligands and complexes as well as
detailed hydrogenation and transfer hydrogenation data are
provided. Crystallographic and geometric data for one synthesis
intermediate and four ruthenium complexes of the type
[RuCl2(PPh3)(L)] and [RuCl2(MeCN)(PPh3)(L)] are given
in the supporting text and in CIF format. This material is
(10) Ahn, K. H.; Cho, C. W.; Baek, H. H.; Park, J.; Lee, S. J. Org.
Chem. 1996, 61, 4937−4943.
(11) (a) Richards, C. J.; Mulvaney, A. W. Tetrahedron: Asymmetry
1996, 7, 1419−1430. (b) Vorbruggen, H.; Krolikiewicz, K. Tetrahedron
̈
Lett. 1981, 22, 4471−4474.
(12) Sawamura, M.; Hamashima, H.; Sugawara, M.; Kuwano, R.; Ito,
Y. Organometallics 1995, 14, 4549−4558.
(13) Coumbe, T.; Lawrence, N. J.; Muhammad, F. Tetrahedron Lett.
1994, 35, 625−628.
(14) Yuan, Y.; Raabe, G.; Bolm, C. J. Organomet. Chem. 2005, 690,
5747−5752.
AUTHOR INFORMATION
■
Corresponding Author
(15) (a) Lamac, M.; Cisarova, I.; Stepnicka, P. J. Organomet. Chem.
2005, 690, 4285−4301. (b) Sebesta, R.; Toma, S.; Salisova, M. Eur. J.
Org. Chem. 2002, 692−695.
Notes
(16) Maciejewski, L. A.; Goetgheluck, S. J.; Delacroix, O. A.; Brocard,
J. S. Tetrahedron: Asymmetry 1996, 7, 1573−1576.
The authors declare no competing financial interest.
(17) (a) Li, H.; Cheng, H.; Seow, A.; Loh, T. Tetrahedron Lett. 2007,
48, 2209−2211. (b) Taylor, C. J.; Roca, F. X.; Richards, C. J. Synlett
2005, 2159−2162. (c) Fukuzawa, S.; Fujimoto, K. Synlett 2001, 1275−
1277. (d) Fukuzawa, S.; Tsuchiya, D.; Sasamoto, K.; Hirano, K.;
Ohtaguchi, M. Eur. J. Org. Chem. 2000, 2877−2883. (e) Fukuzawa, S.;
Kato, H. Synlett 1998, 727−728. (f) Malfait, S.; Pelinski, L.; Brocard, J.
Tetrahedron: Asymmetry 1998, 9, 2207−2210.
ACKNOWLEDGMENTS
■
The authors thank the Austrian Science Foundation FWF
(project P23376-N19) as well as Solvias AG for their strong
support of this work and UMICORE for a generous gift of
metal complexes.
(18) Omedes, M.; Gomez-Sal, P.; Andries, J.; Moyano, A.
Tetrahedron 2008, 64, 3953−3959.
REFERENCES
■
(19) Hayashi, T.; Mise, T.; Fukushima, M.; Kagotani, M.; Nagashima,
N.; Hamada, Y.; Matsumoto, A.; Kawakami, S.; Konishi, M.; Yamamoto,
K.; Kumada, M. Bull. Chem. Soc. Jpn. 1980, 53, 1138−1151.
(20) Schuecker, R.; Weissensteiner, W.; Mereiter, K.; Lotz, M.;
Spindler, F. Organometallics 2010, 29, 6443−6458.
(21) Marr, G.; Wakefield, B. J.; White, T. M. J. Organomet. Chem.
1975, 88, 357−361.
(22) Lamac, M.; Stepnicka, P. Inorg. Chem. Commun. 2006, 9, 319−321.
(23) (a) Ikariya, T.; Blacker, A. J. Acc. Chem. Res. 2007, 40, 1300−
1308. (b) Clapham, S. E.; Hadzovic, A.; Morris, R. H. Coord. Chem.
Rev. 2004, 248, 2201−2237. (c) Noyori, R.; Hashiguchi, S. Acc. Chem.
Res. 1997, 30, 97−102.
(1) (a) Zhou, Y. G.; Hou, X. L. In Chiral Ferrocenes in Asymmetric
Catalysis; Dai, L. X.; Hou, X. L., Eds.; Wiley-VCH: Weinheim, 2010;
pp 97−147. (b) Miyake, Y.; Nishibayashi, Y.; Uemura, S. Synlett 2008,
1747−1758. (c) Hargaden, G. C.; Guiry, P. J. Chem. Rev. 2009, 109,
2505−2550. (d) McManus, H. A.; Guiry, P. J. Chem. Rev. 2004, 104,
4151−4202.
(2) (a) von Matt, P.; Pfaltz, A. Angew. Chem., Int. Ed. 1993, 32, 566−
568. (b) Sprinz, J.; Helmchen, G. Tetrahedron Lett. 1993, 34, 1769−
1772. (c) Dawson, G. J.; Frost, C. G.; Williams, J. M. J.; Coote, S. J.
Tetrahedron Lett. 1993, 34, 3149−3150.
(3) (a) Richards, C. J.; Damalidis, T.; Hibbs, D. E.; Hursthouse, M. B.
Synlett 1995, 74−76. (b) Richards, C. J.; Hibbs, D. E.; Hursthouse, M.
B. Tetrahedron Lett. 1995, 36, 3745−3748. (c) Nishibayashi, Y.;
Uemura, S. Synlett 1995, 79−81. (d) Nishibayashi, Y.; Segawa, K.;
Ohe, K.; Uemura, S. Organometallics 1995, 14, 5486−5487. (e) Park,
J.; Lee, S.; Ahn, K. H.; Cho, C. W. Tetrahedron Lett. 1995, 36, 7263−
7266. (f) Zhang, W.; Adachi, Y.; Hirao, T.; Ikeda, I. Tetrahedron:
Asymmetry 1996, 7, 451−460.
(4) (a) Madrigal, C. A.; Garcia-Fernandez, A.; Gimeno, J.; Lastra, E. J.
Organomet. Chem. 2008, 693, 2535−2540. (b) Bolm, C.; Xiao, L.;
Kesselgruber, M. Org. Biomol. Chem. 2003, 1, 145−152. (c) Nishibaya-
shi, Y.; Takei, I.; Uemura, S.; Hidai, M. Organometallics 1999, 18,
2291−2293. (d) Arikawa, Y.; Ueoka, M.; Matoba, K.; Nishibayashi, Y.;
Hidai, M.; Uemura, S. J. Organomet. Chem. 1999, 572, 163−168.
(e) Du, X. D.; Dai, L. X.; Hou, X. L.; Xia, L. J.; Tang, M. H. Chin. J.
Chem. 1998, 16, 90−93. (f) Sammakia, T.; Stangeland, E. L. J. Org.
Chem. 1997, 62, 6104−6105.
(5) Naud, F.; Malan, C.; Spindler, F.; Ruggeberg, C.; Schmidt, A. T.;
̈
Blaser, H. U. Adv. Synth. Catal. 2006, 348, 47−50.
4250
dx.doi.org/10.1021/om300188g | Organometallics 2012, 31, 4241−4250