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Journal of the Brazilian Chemical Society

Print version ISSN 0103-5053

Abstract

SHU, Kobayashi; HAMADA, Tomoaki; NAGAYAMA, Satoshi  and  MANABE, Kei. Asymmetric catalysis in aqueous media: use of metal-chiral crown ethers as efficient chiral Lewis acid catalysts in asymmetric aldol reactions. J. Braz. Chem. Soc. [online]. 2001, vol.12, n.5, pp. 627-633. ISSN 0103-5053.  http://dx.doi.org/10.1590/S0103-50532001000500006.

Metal-chiral crown ether complexes have been developed as efficient chiral Lewis acid catalysts for asymmetric aldol reactions of silyl enol ethers with aldehydes in aqueous media. While many excellent catalytic asymmetric reactions have been developed recently, most of them have to be carried out under strictly anhydrous conditions in organic solvents. This is probably due to the instability of many catalysts and/or intermediates in the presence of even a small amount of water. To address this issue, we searched for metal-crown ether complexes on the basis of our "multi-coordination" hypothesis, and found that lead(II) and lanthanide(III) catalysts worked well as chiral Lewis acids in aqueous media. To the best of our knowledge, these are the first examples of chiral crown-based Lewis acids that can be successfully used in catalytic asymmetric reactions. The catalysts have been characterized by X-ray diffraction, and their unique structures as chiral catalysts have been revealed. Use of water as a solvent is essential in these asymmetric catalysis, and the role of water on these reactions to explain the high reactivity and selectivity has been suggested. Another important point is that kinetic studies have shown the possibility that these types of crown ether complexes would be suitable as chiral catalysts employed in aqueous media. In addition, although the catalytic asymmetric aldol reactions are one of the most powerful carbon-carbon bond-forming methodologies and several successful examples have been reported, the use of aprotic anhydrous solvents and low reaction temperatures (-78 °C) has been needed in almost all successful cases. On the other hand, the present reactions proceeded smoothly at -10-0 °C in water-alcohol solutions while retaining high levels of diastereo- and enantioselectivities.

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