Published on Web 06/20/2003
Solvent-Free Asymmetric Olefin Hydroformylation Catalyzed
by Highly Cross-Linked Polystyrene-Supported
(R,S)-BINAPHOS-Rh(I) Complex
Fumitoshi Shibahara,†,⊥ Kyoko Nozaki,*,†,‡ and Tamejiro Hiyama§
Contribution from ConVersion and Control by AdVanced Chemistry, PRESTO, Japan Science
and Technology, 1-8, Honcho 4-Chome, Kawaguchi 332-0012, Japan, Department of
Chemistry and Biotechnology, Graduate School of Engineering, The UniVersity of Tokyo,
Hongo, Bunkyo-ku, Tokyo 113-8656, Japan, and Department of Material Chemistry,
Graduate School of Engineering, Kyoto UniVersity, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan
Abstract: Using an (R,S)-BINAPHOS-Rh(I) catalyst that is covalently anchored to a highly cross-linked
polystyrene support, asymmetric hydroformylation of olefins was performed in the absence of organic
solvents. The reaction of cis-2-butene, a gaseous substrate, provided (S)-2-methylbutanal with 100%
2
regioselectivity and 82% ee upon treatment with H (12 atm) and CO (12 atm) in a batchwise reactor
equipped with a fixed bed. The polymer-supported catalyst was applicable to a continuous vapor-flow column
reactor, and thus, 3,3,3-trifluoropropene was converted into (S)-2-trifluoromethylpropanal with an iso/normal
ratio of 95/5 and 90% ee. Less volatile olefins, such as styrene, vinyl acetate, 1-alkenes, and fluorinated
alkenes, were successfully converted into the corresponding isoaldehydes with high ee values, when they
2
were injected through a supercritical CO -flow column reactor. Successive injection of a series of olefins
realized the conversion of an olefin library into an optically active aldehyde library.
ilton3a and for other reactions by Leitner.3b-c Recently, van den
Introduction
Broeke reported hydrogenation of 1-alkenes in a continuous
scCO2 flow system using a bulky Rh catalyst bearing long per-
fluoroalkyl chains. The catalyst was separated by a micropor-
Despite many advantages over heterogeneous catalysis in
terms of catalyst selectivity and activity, homogeneous catalysis
has two major drawbacks: separation of catalyst from products
and use of organic solvents to suppress precipitation of catalyst
metal. Separation of products and catalysts are performed most
conveniently by phase separation. Thus, immobilization of or-
ganometallic catalysts on organic polymers or on silica gel has
been considered to be one of the major challenges in homoge-
4
ous silica-membrane filter. These systems are directly ap-
plicable to a large-scale catalysis process. On the other hand,
less attention has been paid on asymmetric catalysis in these
systems. This is not surprising, since asymmetric catalysis
usually needs finely tuned reaction conditions. Among all, sol-
vent stabilization of the catalyst complex is usually an essential
factor. For example, when scCO2 is used as a solvent, enantio-
1
neous catalysis.
Although most supported catalysts are used in suspension with
organic solvents, the same reactions may be carried out without
organic solvents under flow-reaction systems. Poliakoff and van
Leeuwen prepared and used silica-supported Rh-xantphos
complexes for hydroformylation of 1-alkenes under continuous
flow of supercritical carbon dioxide (scCO2) without any metal
5
-8
selectivity drops in many cases.
In 1993, an unsymmetrical phosphine-phosphite ligand,
R,S)-BINAPHOS, was invented and shown to attain excellent
(
enantioselectivities in asymmetric hydroformylation of a wide
range of prochiral olefins upon use in combination with
9
2
rhodium(I). Although the Rh(I) complexes of bis-phosphorus
leaching. Another approach for the scCO2 continuous flow
ligands, all derived from D-(+)-glucose, were reported as another
process is the use of an ionic liquid as an immobilizing phase
for catalyst, as reported for hydroformylation by Cole-Ham-
(
3) (a) Sellin, M. F.; Webb, P. B.; Cole-Hamilton, D. J. Chem. Commun. 2001,
781. (b) B o¨ smann, A.; Franci o´ , G.; Janssen, E.; Solinas, M.; Leitner, W.;
Wasserscheid, P. Angew. Chem., Int. Ed. 2001, 40, 2697. (c) Reetz, M. T.;
Wiesenh o¨ fer, W.; Franci o´ , G.; Leitner, W. Chem. Commun. 2002, 992.
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Deelman, B.-J.; van Koten, G.; Keurentjes, J. T. F. Angew. Chem. Int. Ed.
2001, 40, 4473.
†
Japan Science and Technology.
The University of Tokyo.
Kyoto University.
Present address: Department of Chemistry, Gifu University, Yanagido,
‡
§
(
⊥
Gifu 501-1193 Japan.
(
1) (a) de Miguel, Y. R. J. Chem. Soc., Perkin Trans. 1 2000, 4213. (b) de
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10.1021/ja034447u CCC: $25.00 © 2003 American Chemical Society
J. AM. CHEM. SOC. 2003, 125, 8555-8560
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