Enantioselective Aldol Reactions of Aliphatic Aldehydes with Singh’s Catalyst

Abstract

Aldols from aliphatic aldehydes had been synthesized enantioselectively using Singh’s catalyst. Self and crossed aldol reactions with several linear aldehydes were performed.

Share and Cite:

H. Kylmälä, A. Neuvonen and R. Jokela, "Enantioselective Aldol Reactions of Aliphatic Aldehydes with Singh’s Catalyst," International Journal of Organic Chemistry, Vol. 3 No. 2, 2013, pp. 162-167. doi: 10.4236/ijoc.2013.32020.

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1] T. D. Machajewski and C.-H. Wong, “The Catalytic Asymmetric Aldol Reaction,” Angewandte Chemie International Edition, Vol. 39, No. 8, 2000, pp. 1352-1375. doi:10.1002/(SICI)1521-3773(20000417)39:8<1352::AID-ANIE1352>3.0.CO;2-J
[2] A. B. Northrup and D. W. C. Mac-Millan, “The First Direct and Enantioselective Cross-Aldol Reaction of Aldehydes,” Journal of the American Chemical Society, Vol. 124, No. 24, 2002, pp. 6798-6799. doi:10.1021/ja0262378
[3] P. Pihko and A. Erkkilä, “Enantioselective Synthesis of Prelactone B Using a Proline-Catalyzed Crossed-Aldol Reaction,” Tetrahedron Letters, Vol. 44, No. 41, 2003, pp. 7607-7609. doi:10.1016/j.tetlet.2003.08.060
[4] C. Pidathala, L. Hoang, N. Vignola and B. List, “Direct Catalytic Asymmetric Enolexo Aldolizations,” Angewandte Chemie International Edition, Vol. 42. No. 24, 2003, pp. 2785-2788. doi:10.1002/anie.200351266
[5] I. K. Mangion, A. B. Northrup and D. W. C. MacMillan, “The Importance of Iminium Geometry Control in Enamine Catalysis: Identification of a New Catalyst Architecture for Aldehyde-Aldehyde Couplings,” Angewandte Chemie International Edition, Vol. 43, No. 48, 2004, pp. 6722-6724. doi:10.1002/anie.200461851
[6] R. I. Storer and D. W. C. MacMillan, “Enantioselective Organocatalytic Aldehyde-Aldehyde Cross-Aldol Couplings. The Broad Utility of α-Thioacetal Aldehydes,” Tetrahedron, Vol. 60, No. 35, 2004, pp. 7705-7714. doi:10.1016/j.tet.2004.04.089
[7] A. B. Northrup, I. K. Mangion, F. Hettche and D. W. C. MacMillan, “Enantioselective Organocatalytic Direct Aldol Reactions of α-Oxyaldehydes: Step One in a TwoStep Synthesis of Carbohydrates,” Angewandte Chemie International Edition, Vol. 43, No. 16, 2004, pp. 21522154. doi:10.1002/anie.200453716
[8] A. Córdova, “Direct Catalytic Asymmetric Cross-Aldol Reactions in Ionic Liquid Media,” Tetrahedron Letters, Vol. 45, No. 20, 2004, pp. 3949-3952. doi:10.1016/j.tetlet.2004.03.080
[9] S. Aratake, T. Itoh, T. Okano, T. Usui, M. Shoji and Y. Hayashi, “Small Organic Molecule in Enantioselective, Direct Aldol Reaction “in Water”,” Chemical Communications, No. 24, 2007, pp. 2524-2526.
[10] Y. Hayashi, S. Samanta, T. Itoh and H. Ishikawa, “Asymmetric, Catalytic, and Direct Self-Aldol Reaction of Acetaldehyde Catalyzed by Diarylprolinol,” Organic Letters, Vol. 10, No. 24, 2008, pp. 5581-5583. doi:10.1021/ol802438u
[11] Y. Chi, S. T. Scroggins, E. Boz and J. M. J. Fréchet, “Control of Aldol Reaction Pathways of Enolizable Aldehydes in an Aqueous Environment with a Hyperbranched Polymeric Catalyst,” Journal of the American Chemical Society, Vol. 130, No. 51, 2008, pp. 1728717289. doi:10.1021/ja806584q
[12] M. Markert, U. Scheffler and R. Mahrwald, “Asymmetric Histidine-Catalyzed Cross-Aldol Reactions of Enolizable Aldehydes: Access to Defined Configured Quaternary Stereogenic Centers,” Journal of the American Chemical Society, Vol. 131, No. 46, 2009, pp. 16642-16643. doi:10.1021/ja907054y
[13] Y. Hayashi, Y. Yasui, T. Kawamura, M. Kojima and H. Ishikawa, “One-Pot Synthesis of Chiral α-Substituted β,γ-Epoxy Aldehyde Derivatives through an Asymmetric Aldol Reaction of Chloroacetaldehyde,” Angewandte Chemie International Edition, Vol. 50, No. 12, 2011, pp. 2804-2807. doi:10.1002/anie.201005577
[14] T. Kano, H. Sugimoto and K. Maruoka, “Efficient Organocatalytic Cross-Aldol Reaction between Aliphatic Aldehydes through Their Functional Differentiation,” Journal of the American Chemical Society, Vol. 133, No. 45, 2011, pp. 18130-18133. doi:10.1021/ja208873k
[15] M. S. Sarkar, Y. Taira, A. Nakano, K. Takashaki, J. Ishihara and S. Hatakeyama, “Organocatalytic Asymmetric Synthesis of Quinine and Quindine,” Tetrahedron Letters, Vol. 52, No. 8, 2011, pp. 923-927. doi:10.1016/j.tetlet.2010.12.066
[16] C.-S. Da, L.-P. Che, Q.-P. Guo, F.-C. Wu, X. Ma and Y.-N. Jia, “2,4-Dinitrophenol as an Effective Cocatalyst: Greatly Improving the Activities and Enantioselectivities of Primary Amine Organocatalysts for Asymmetric Aldol Reactions,” Journal of Organic Chemistry, Vol. 74, No. 6, 2009, pp. 2541-2546. doi:10.1021/jo802758b
[17] M. Raj, Vishnumaya, S. K. Ginotra and V. K. Singh, “Highly Enantioselective Direct Aldol Reaction Catalyzed by Organic Molecules,” Organic Letters, Vol. 8, No. 18, 2006, pp. 4097-4099. doi:10.1021/ol0616081
[18] For a review: S. Mukherjee, J. W. Yang, S. Hoffmann and B. List, “Asymmetric Enamine Catalysis,” Chemical Reviews, Vol. 107, No. 12, 2007, pp. 5471-5569. doi:10.1021/cr0684016
[19] V. Maya, M. Raj and V. K. Singh, “Highly Enantioselective Organocatalytic Direct Aldol Reaction in an Aqueous Medium,” Organic Letters, Vol. 9, No. 13, 2007, pp. 2593-2595. doi:10.1021/ol071013l
[20] L. Song, X. Chen, S. Zhang, H. Zhang, P. Li, W. Duan and W. Wang, “An Organocatalytic Approach to the Construction of Chiral Oxazolidinone Rings and Application in the Synthesis of Antibiotic Linezolid and Its Analogues,” Organic Letters, Vol. 10, No. 23, 2008, pp. 5489-5492. doi:10.1021/ol802333n
[21] M. Raj, V. Maya and V. K. Singh, “Highly Efficient Small Organic Molecules for Enantioselective Direct Aldol Reaction in Organic and Aqueous Media,” Journal of Organic Chemistry, Vol. 74, No. 11, 2009, pp. 4289-4297. doi:10.1021/jo900548f
[22] M. Raj and V. K. Singh, “Organocatalytic Reactions in Water,” Chemical Communications, No. 44, 2009, pp. 6687-6703.
[23] K. Baer, M. Krauβer, E. Burda, W. Hummel, A. Berkessel and H. Gröger, “Sequential and Modular Synthesis of Chiral 1,3-Diols with Two Stereogenic Centers: Access to All Four Stereoisomers by Combination of Organoand Biocatalysis,” Angewandte Chemie International Edition, Vol. 48, No. 49, 2009, pp. 9355-9358. doi:10.1002/anie.200900582
[24] H. Zhang, S. Zhang, L. Liu, G. Luo, W. Duan and W. Wang, “Synthesis of Chiral 3-Substituted Phthalides by a Sequential Organocatalytic Enantioselective Aldol-Lactonization Reaction. Three-Step Synthesis of (S)-(–)-3-Butylpthalide,” Journal of Organic Chemistry, Vol. 75, No. 2, 2010, pp. 368-374. doi:10.1021/jo902118x
[25] G. Rulli, N. Duangdee, K. Baer, W. Hummel, A. Berkessel and H. Gröger, “Direction of Kinetically versus Thermodynamically Controlled Organocatalysis and Its Application in Chemoenzymatic Synthesis,” Angewandte Chemie International Edition, Vol. 50, No. 34, 2011, pp. 7944-7947. doi:10.1002/anie.201008042
[26] Z. Tang, F. Jiang, L.-T. Yu, X. Cui, L.-Z. Gong, A.-Q. Mi, Y.-Z. Jiang and Y.-D. Wu, “Novel Small Organic Molecules for a Highly Enantioselective Direct Aldol Reaction,” Journal of the American Chemical Society, Vol. 125, No. 18, 2003, pp. 5262-5263. doi:10.1021/ja034528q
[27] S. Sulzer-Mossé and A. Alexakis, “Chiral Amines as Organocatalysts for Asymmetric Conjugate Addition to Nitroolefins and Vinyl Sulfones via Enamine Activation,” Chemical Communications, No. 30, 2007, pp. 3123-3135.
[28] H. Flink, T. Putkonen and R. Jokela, “Microwave-Assisted Selective Protection of Glutaraldehyde and Its Symmetrical Derivatives as Monoacetals and Thioacetals,” Tetrahedron, Vol. 66, No. 4, 2010, pp. 887-890. doi:10.1016/j.tet.2009.11.107
[29] H. Flink and R. Jokela, “Microwave-Assisted Total Synthesis of Tangutorine,” Tetrahedron, Vol. 68, No. 20, 2012, pp. 3811-3814. doi:10.1016/j.tet.2012.03.068

Copyright © 2024 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.