Simple Reduction of Hydantoins with Sodium Borohydride

DOI: 10.4236/ijoc.2014.45031   PDF   HTML   XML   3,392 Downloads   4,396 Views   Citations

Abstract

The reduction of various hydantoins with sodium borohydride gave the corresponding 4-hydroxy- 2-imidazolidinones in high yields. In contrast, reduction employing a boron trifluoride etherate-sodium borohydride system generated 2-imidazolidinones. In both reductions, the reactivity of the hydantoin was dependent on its substituents. The Lewis acid-promoted reactions of a 4-hydroxy-2-imidazolidinone with nucleophiles were also investigated.

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Yamaguchi, J. , Shibuta, E. and Oishi, Y. (2014) Simple Reduction of Hydantoins with Sodium Borohydride. International Journal of Organic Chemistry, 4, 286-291. doi: 10.4236/ijoc.2014.45031.

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1] Yamaguchi, J., Harada, M., Narushima, T., Saitoh, A., Nozaki, K., and Suyama, T. (2005) Diastereoselective Conjugate Addition of 1-(a,b-Unsaturated acyl)hydantoin with Nucleophiles. Tetrahedron Letters, 46, 6411-6415.
http://dx.doi.org/10.1016/j.tetlet.2005.07.116
[2] Chavan, S.P., Tejwani, R.B. and Ravindranathan, T. (2001) A Switch of Reactivity Profile in Ionic Intramolecular Annulation Reactions: A Short and Efficient Synthesis of D-(+)-Biotin. Journal of the Organic Chemistry, 66, 6197-6201.
http://dx.doi.org/10.1021/jo015730j
[3] Chavan, S.P., Chittiboyina, A.G., Ravindranathan, T., Kamat, S.K. and Kalkote, U.R. (2005) Diastereoselective Amidoalky- lation of (3S,7aR)-6-Benzyl-7-hydroxy-3-phenyltetrahydro-5H-imiazo[1,5-c][1,3]thiazol-5-one: A Short and Highly Efficient Synthesis of (+)-Biotin. Journal of the Organic Chemistry, 70, 1901-1903.
http://dx.doi.org/10.1021/jo0488107
[4] Wilk, I.J. and Close, W.J. (1950) The Action of Lithium Aluminum Hydride on 3-Methyl-5-phenylhydantoin and 5- Phenylhydantoin. Journal of the Organic Chemistry, 15, 1020-1022.
http://dx.doi.org/10.1021/jo01151a017
[5] Li, C.-D., Lee, M.H. and Sartorelli, A.C. (1979) Synthesis and Biological Evaluation of Tetramisole Analogues as Inhibitors of Alkaline Phosphatase of the 6-Thiopurine-Resistant Tumor Sarcoma 180/TG1. Journal of Medicinal Chemistry, 22, 1030-1033.
http://dx.doi.org/10.1021/jm00195a003
[6] Marshall, F.J. (1956) Lithium Aluminum Hydride Reduction of Some Hydantoins, Barbiturates and Thiouracils. The Journal of American Chemical Society, 78, 3696-3697.
http://dx.doi.org/10.1021/ja01596a038
[7] Cortes, S. and Kohn, H. (1983) Selective Reductions of 3-Substituted Hydantoins to 4-Hydroxy-2-imidazolidinones and Vicinal Diamines. Journal of the Organic Chemistry, 48, 2246-2254.
http://dx.doi.org/10.1021/jo00161a021
[8] Cortes, S. and Kohn, H. (1983) Selective Reductions of 3-Substituted Hydantoins to 4-Hydroxy-2-imidazolidinones and Vicinal Diamines. Journal of the Organic Chemistry, 48, 2246-2254.
http://dx.doi.org/10.1021/jo00161a021
[9] Liao, Z.-K. and Kohn, H. (1984) Synthesis of Substituted 2-Imidazolidinones and Annelated Hydantoin via Amidoalkylation Transformations. Journal of the Organic Chemistry, 49, 4745-4752.
http://dx.doi.org/10.1021/jo00199a001
[10] Moolenaar, M.J., Speckamp, W.N., Hiemstra, H., Poetsch, E. and Casutt, M. (1995) Synthesis of D-(+)-Biotin through Selective Ring Closure of N-Acyliminium Silyl Enol Ether. Angewandte Chemie International Edition, 34, 2391-2393.
http://dx.doi.org/10.1002/anie.199523911
[11] Drewes, S.E., Malissar, D.G.S. and Roos, G.H.P. (1993) Ephedrine-Derived Imidazolidin-2-Ones. Broad Utility Chiral Auxiliaries in Asymmetric Synthesis. Chemische Berichte, 126, 2663-2673.
http://dx.doi.org/10.1002/cber.19931261216
[12] Taguchi, T., Shibuya, A., Sasaki, H., Endo, J., Morikawa, T. and Shiro, M. (1994) Asymmetric Synthesis of Difluorocyclopropanes. Tetrahedron: Asymmetry, 5, 1423-1426.
http://dx.doi.org/10.1016/0957-4166(94)80101-0
[13] Bongini, A., Cardillo, G., Gentilucci, L. and Tomasini, C. (1997) Synthesis of Enantiomerically Pure Aziridine-2-Imides by Cyclization of Chiral 3’-Benzyloxyamino Imide Enolates. Journal of Organic Chemistry, 62, 9148-9153.
http://dx.doi.org/10.1021/jo971254e
[14] Guillena, G. and Najera, C. (1998) PTC and Organic Bases-LiCl Assisted Alkylation of Imidazolidinone-Glycine Iminic Derivatives for the Asymmetric Synthesis of α-Amino Acids. Tetrahedron: Asymmetry, 9, 3935-3938.
http://dx.doi.org/10.1016/S0957-4166(98)00402-9
[15] Guillena, G. and Najera, C. (2000) 1,5-Dimethyl-4-Phenylimidazolidin-2-One-Derived Iminic Glycinimides: Useful New Reagents for Practical Asymmetric Synthesis of α-Amino Acids. Journal of Organic Chemistry, 65, 7310-7322.
http://dx.doi.org/10.1021/jo000321t
[16] Kim, T.H. and Lee, G.-J. (1999) Regiocontrolled Cyclization Reaction of N-(2-Hydroxy)Ureas by Transfer of Activation: One-Pot Synthesis of 2-Imidazolidinones. Journal of Organic Chemistry, 64, 2941-2943.
http://dx.doi.org/10.1021/jo9820061
[17] Kim, T.H. and Lee, G.-J. (2000) L-Valinol and L-Phenylalaninol-Derived 2-Imidazolidinones as Chiral Auxiliaries in Asymmetric Aldol Reactions. Tetrahedron Letters, 41, 1505-1508.
http://dx.doi.org/10.1016/S0040-4039(99)02325-4
[18] Nadir, U.K., Krishna, R.V. and Singh, A. (2005) A New and Facile Route for the Synthesis of Chiral 1,2-Diamines and 2,3-Diamino Acids. Tetrahedron Letters, 46, 479-482.
http://dx.doi.org/10.1016/j.tetlet.2004.11.088
[19] Tschantz, M.A., Burgess, L.E. and Meyers, A.I. (1996) (S)-(-)-5-Heptyl-2-pyrrolidineone. Chiral Bicyclic Lactams as Templates for Pyrrolidines and Pyrrolidinones. Organic Synthesis, 73, 221-230.

  
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