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Recyclable Cyclohexanediamine Derivatives as Organocatalysts: Organocatalytic Reduction with Trichlorosilane and Aldol Reaction

DOI: 10.4236/ijoc.2013.34034, PP. 240-242

Keywords: Aldol Reaction, Cyclohexanediamine, Organocatalysis, Recyclable, Reduction

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Abstract:

Reduction of ketimine with trichlorosilane was carried out using bisformamide catalyst 1a derived from cyclohexanediamine to give the corresponding product in 81% yield with 39% ee. Deprotection of the formyl groups of the catalysts 1 gave the corresponding diamines 2 which were utilized in aldol reaction of acetone with 4-nitrobenzaldehyde. The reaction using 2b in brine afforded the aldol adduct in 81% yield with 29% ee.

 

References

[1]  A. Berkessel and H. Groer, Eds., “Asymmetric Organocatalysis: From Biomimetic Concepts to Applications in Asymmetric Synthesis,” Wiley-VCH, Weinheim, 2005.
http://dx.doi.org/10.1002/3527604677
[2]  P. I. Dalko, Ed., “Enantioselective Organocatalysis: Reactions and Experimental Procedures,” Wiley-VCH, Weinheim, 2007.
[3]  B. List, Ed., “Asymmetric Organocatalysis,” Springer, Berlin, 2009.
http://dx.doi.org/10.1007/978-3-642-02815-1
[4]  K. Ishimaru, K. Ono, Y. Tanimura and T. Kojima, “Novel chiral Bisformamide-Promoted Asymmetric Allylation of Benzaldehyde with Allyltrichlorosilane,” Synthetic Communications, Vol. 41, No. 24, 2011, pp. 3627-3634.
http://dx.doi.org/10.1080/00397911.2010.519841
[5]  Y. Tanimura and K. Ishimaru, “Asymmetric Allylation Reactions of Aromatic Aldehydes with Allyltrichlorosilane Catalyzed by Chiral Bisformamide-Type Organocatalysts,” Tetrahedron: Asymmetry, Vol. 23, No. 5, 2012, pp. 345-349.
http://dx.doi.org/10.1016/j.tetasy.2012.02.015
[6]  R. A. Benkeser and D. C. Snyder, “Trichlorosilane-Imine Complexes. A New Method for the Reduction of Imines to Amines,” Journal of Organometallic Chemistry, Vol. 225, No. 1, 1982, pp. 107-115.
http://dx.doi.org/10.1016/S0022-328X(00)86814-X
[7]  S. Kobayashi, M. Yasuda and I. Hachiya, “Trichlorosilane-Dimethylformamide (Cl3SiH-DMF) as an Efficient Reducing Agent. Reduction of Aldehydes and Imines and Reductive Amidation of Aldehydes under Mild Conditions Using Hypervalent Hydridosilicates,” Chemistry Letters, No. 5, 1996, pp. 407-408.
http://dx.doi.org/10.1246/cl.1996.407
[8]  F. Iwasaki, O. Onomura, K. Mishima, T. Maki and Y. Matsumura, “Catalytic Activation of Trichlorosilane for Efficient and Stereoselective Reduction of Ketones,” Tetrahedron Letters, Vol. 40, No. 42, 1999, pp. 7507-7511.
http://dx.doi.org/10.1016/S0040-4039(99)01554-3
[9]  C. Baudequin, D. Chaturvedi and S. B. Tsogoeva, “Organocatalysis with Chiral Formamides: Asymmetric Allylation and Reduction of Imines,” European Journal of Organic Chemistry, No. 16, 2007, pp. 2623-2629.
http://dx.doi.org/10.1002/ejoc.200700058
[10]  R. Mahrwald, Ed., “Modern Aldol Reactions,” Wiley-VCH, Weinheim, 2004.
http://dx.doi.org/10.1002/9783527619566
[11]  J. C. Sheehan and D.-D. H. Yang, “The Use of N-Formylamino Acids in Peptide Synthesis,” Journal of the American Chemical Society, Vol. 80, No. 5, 1958, pp. 1154-1158. http://dx.doi.org/10.1021/ja01538a036
[12]  T. Kanemitsu, A. Umehara, R. Haneji, K. Nagata and T. Itoh, “A Simple Proline-Based Organocatalyst for the Enantioselective Reduction of Imines Using Trichlorosilane as a Reductant,” Tetrahedron, Vol. 68, No. 20, 2012, pp. 3893-3898.
http://dx.doi.org/10.1016/j.tet.2012.03.035
[13]  Z. Tang, Z.-H. Yang, X.-H. Chen, L.-F. Cun, A.-Q. Mi, Y.-Z. Jiang and L.-Z. Gong, “A Highly Efficient Organocatalyst for Direct Aldol Reactions of Ketones with Aldehydes,” Journal of the American Chemical Society, Vol. 127, No. 25, pp. 9285-9289.
http://dx.doi.org/10.1021/ja0510156

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