Share This Article:

Stereoselective Aldol Reaction in Aqueous Solution Using Prolinamido-Glycosides as Water-Compatible Organocatalyst

Abstract Full-Text HTML XML Download Download as PDF (Size:2675KB) PP. 20-27
DOI: 10.4236/mrc.2015.41003    4,861 Downloads   5,469 Views   Citations


Prolinamido-glycoside catalyzed asymmetric aldol reaction in aqueous media is reported. The reactions are rapid and highly stereoselective when water is used as solvent. The stereoselectivities were under influence of configurations of a prolyl residue of the catalyst and α-chiral aldehydes. Water soluble prolinamido-glycoside catalysts are easily separable from reaction mixture and can be recycled and re-used several times.

Conflicts of Interest

The authors declare no conflicts of interest.

Cite this paper

Miura, D. and Machinami, T. (2015) Stereoselective Aldol Reaction in Aqueous Solution Using Prolinamido-Glycosides as Water-Compatible Organocatalyst. Modern Research in Catalysis, 4, 20-27. doi: 10.4236/mrc.2015.41003.


[1] Tanaka, F. and Barbas, C.F. (2007) Enantioselective Organocatalysis, Reactions and Experimental Procedures. In: Dalko, P.I., Ed., Weiley-VCH, Weinheim, 19-55.
[2] List, B., Lerner, R.A. and Barbas III, C.F. (2000) Proline-Catalyzed Direct Asymmetric Aldol Reactions. Journal of the American Chemical Society, 122, 2395-2396.
[3] Sakthivel, K., Not, W., Bui, T. and Barbas III, C.F. (2001) Amino Acid Catalyzed Direct Asymmetric Aldol Reactions: A Bioorganic Approach to Catalytic Asymmetric Carbon-Carbon Bond-Forming Reactions. Journal of the American Chemical Society, 123, 5260-5267.
[4] Dickerson, T.J. and Janda, K.D. (2002), Aqueous Aldol Catalysis by a Nicotine Metabolite. Journal of the American Chemical Society, 124, 3220-3221.
[5] Dickerson, T.J., Lovell, T., Meijler, M.M., Noodleman, L. and Janda, K.D. (2004)Nornicotine Aqueous Aldol Reactions: Synthetic and Theoretical Investigations into the Origins of Catalysis. The Journal of Organic Chemistry, 69, 6603-6609.
[6] Pedatella, S., De Nisco, M., Mastroianni, D., Naviglio, D., Nucci, A. and Caputo, R. (2011) Diastereo- and Enantioselective Direct Aldol Reactions in Aqueous Medium: A New Highly Efficient Proline-Sugar Chimeric Catalys, Advanced Synthesis & Catalysis, 353, 1443-1446.
[7] Burroughs, L., Vale, M.E., Gilks, J.A., Forintos, H., Hayes, C.J. and Clarke, P.A. (2010) Efficient Asymmetric Organocatalytic Formation of Erythrose and Threose under Aqueous Conditions. Chemical Communications, 46, 4776-4778.!divAbstract
[8] Maya, V., Raj, M. and Singh, V.K. (2007) Highly Enantioselective Organocatalytic Direct Aldol Reaction in an Aqueous Medium. Organic Letters, 9, 2593-2595.
[9] Ramasastry, S.S.V., Albertshofer, K., Utsumi, N. and Barbas III, C.F. (2008) Water-Compatible Organocatalysts for Direct Asymmetric syn-Aldol Reactions of Dihydroxyacetone and Aldehydes. Organic Letters, 10, 1621-1624.
[10] Kofoed, J., Reymond, J.-L. and Darbre, T. (2005) Prebiotic Carbohydrate Synthesis: Zinc-Proline Catalyzes Direct Aqueous Aldol Reactions of α-Hydroxy Aldehydes and Ketones. Organic & Biomolecular Chemistry, 3, 1850-1855.!divAbstract
[11] Tsutsui, A., Takeda, H., Kimura, M., Fujimoto, T. and Machinami, T. (2007) Novel Enantiocontrol System with Aminoacyl Derivatives of Glucoside as Enamine-Based Organocatalysts for Aldol Reaction in Aqueous Media. Tetrahedron Letters, 48, 5213-5217.
[12] Miura, D., Fujimoto, T., Tsutsui, A. and Machinami, T. (2013) Stereoselective Synthesis of Ketoses by Aldol Reaction Using Water-Compatible Prolinamide Catalysts in Aqueous Media. Synlett, 24, 1501-1504.
[13] Suami, T. (1982) Nitrosourea derivatives, Fr, Demande, Fr 2493318, A1, 19820507.
[14] Jeffs, P.W., Chan, G., Sitrin, R., Holder, N., Roberts, G.D. and DeBrosse, C. (1985) The Structure of Glycolipid Components of the Aridicin Antibiotic Complex. The Journal of Organic Chemistry, 50, 1726-1731.
[15] Schimd, C.R., Bryant, J.D., Dowlatzedah, M., Phillips, J.L., Prather, D.E., Schantz, R.D., Sear, N.L. and Vianco, C.S. (1991) Synthesis of 2,3-O-isopropylidene-D-glyceraldehyde in High Chemical and Optical Purity: Observations on the Development of a Practical Bulk Process. The Journal of Organic Chemistry, 56, 4056-4058.
[16] Wilde, H.D., Clercq, P.D. and Vandewalle, M. (1987) L-(S)-erythrulose a Novel Precursor to L-2,3-O-isopropylidene- C3 Chirons. Tetrahedron Letters, 28, 4757-4758.
[17] Forbes, D.C., Ene, D.G. and Doyle, M.P. (1998) Stereoselective Synthesis of Substituted 5-Hydroxy-1,3-dioxanes. Synthesis, 6, 879-882.
[18] West, B.F., Bhat, K.V. and Zorbach, W.W. (1968) 2-Deoxy Sugars Part XIII. 1,3-Dideoxy-d-erythro-hexulose. Carbohydrate Research, 8, 253-261.
[19] Kito, Y., Kawakishi, S. and Namiki, M. (1980) A Novel Reaction of Sugars with Anion Radical of Carbon Dioxide Produced from Formate. Agricultural and Biological Chemistry, 44, 2695-2701.
[20] Torsell, K.B.G., Hazell, A.C. and Hazell, R.G. (1985) Silylnitronates and NITRILE Oxides in Organic Synthesis. A Novel Route to D,L-deoxysugars. Use of Aluminum Oxide as Solid Phase Base for generation of. Tetrahedron, 41, 5569-5575.
[21] Iwamoto, H., Yoshida, M., Yamamoto, M. and Tanuma, T. (1984) European Patent Applications, EP 123444A1 19841031.
[22] Tamura, T., Iwamoto, H., Yoshida, M. and Yamamoto, M. (1985) Japanese Kokai Tokkyo Koho, JP60172996 A19850906.
[23] Majewski, M. and Nowak, P.J. (2000) Aldol Addition of Lithium and Boron Enolates of 1,3-Dioxan-5-ones to Aldehydes. A New Entry into Monosaccharide Derivatives. The Journal of Organic Chemistry, 65, 5152-5160.
[24] Majewski, M. and Nowak, P. (1999) Stereoselective Synthesis of Protected Ketohexoses via Aldol Reaction of Chiral Dioxanone Enolate. Synlett, 9, 1447-1449.
[25] Grondal, C. and Enders, D. (2006) Direct Asymmetric Organocatalytic de Novo Synthesis of Carbohydrates. Tetrahedron, 62, 329-337.
[26] Suri, J.T., Mitsumori, S., Albertshofer, K., Tanaka, F. and Barbas III, C.F. (2006) Dihydroxyacetone Variants in the Organocatalytic Construction of Carbohydrates: Mimicking Tagatose and Fuculose Aldolases. The Journal of Organic Chemistry, 71, 3822-3828.
[27] Hann, R.M., Tilden, E.B. and Hudson, C.S.J. (1938) The Oxidation of Sugar Alcohols by Acetobacter suboxydans. Journal of the American Chemical Society, 60, 1201-1203.
[28] Hochster, R.M. and Watson, R.W. (1953) XYLOSE ISOMERASE. Journal of the American Chemical Society, 75, 3284-3285.
[29] Bean, R.C. and Hassid, W.Z.J. (1955) Synthesis of Disaccharides with Pea Preparations. Journal of the American Chemical Society, 77, 5737-5738.
[30] Hollmann, S. and Touster, O. (1956) An Enzymatic Pathway from L-Xylulose to D-Xylulose. Journal of the American Chemical Society, 78, 3544-3545.
[31] Suzuki, K., Yuki, Y. and Mukaiyama, T. (1981) The Stereoselective Synthesis of D-Ribulose. Chemistry Letters, 11, 1529-1532.
[32] Drueckhammer, D.G., Durrwachter, J.R., Pederson, R.L., Richard, L., Crans, D.C., Daniels, L. and Wong, C.H. (1989) Reversible and in Situ Formation of Organic Arsenates and Vanadates as Organic Phosphate Mimics in Enzymatic Reactions: Mechanistic Investigation of Aldol Reactions and Synthetic Applications. The Journal of Organic Chemistry, 54, 70-77.
[33] Vuorien, T. and Serianni, A.S. (1991) Synthesis of D-erythro-2-pentulose and D-threo-2-pentulose and Analysis of the 13C- and 1H-n.m.r. Spectra of the 1-13C- and 2-13C-Substituted Sugars. Carbohydrate Research, 209, 13-31.
[34] Fisher, M., Kaehling, H. and Schmid, W. (2011) Gram Scale Synthesis of 3-Fluoro-1-hydroxyacetone Phosphate: A Novel Donor Substrate in Rabbit Muscle Aldolase-Catalyzed Aldol Reactions. Chemical Communications, 47, 6647- 6649.!divAbstract

comments powered by Disqus

Copyright © 2018 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.