Ti(IV) Chloride-Promoted Diastereoselective Conjugate Addition of 1-Enoyl-5-substituted Hydantoins with Allyltrimethylsilane

Jun-ichi Yamaguchi, Kanako Nozaki Abe, Takayuki Suyama

Department of Applied Chemistry, Faculty of Engineering, Kanagawa Institute of Technology, Atsugi, Japan.

DOI: 10.4236/ijoc.2012.24045                

Abstract

Diastereoselective conjugate addition of 1-enoyl-5-substituted hydantoins with allyltrimethylsilane in the presence of Ti(IV) chloride proceeded to give the corresponding allyl adducts in high yield and high diastereoselectivity. In order to determine the absolute configuration on the β-position of the acyl group, the hydantoin was removed by hydrolysis of the allyl adducts with a base to give the corresponding carboxylic acid. It was found that the absolute configuration was S on the basis of specific rotation.

Keywords

Hydantoin; Conjugate Addition; Lewis Acid; Allyltrimethylsilane

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1]	R. M. Coates and S. E. Denmark, “Handbook of Reagents for Organic Synthesis: Reagents, Auxiliaries, and Catalysts for C-C Bond Formation,” John Willey & Sons Ltd., Chichester, 1999.
[2]	J. Yamaguchi, M. Harada, T. Kondo, T. Noda, and T. Suyama, “A Facile Method for Preparation of Optically Active Hydantoin,” Chemistry Letters, Vol. 32, No. 4, 2003, pp. 372-373. doi:10.1246/cl.2003.372
[3]	J. Yamaguchi, M. Harada, T. Narushima, A. Saitoh, K. Nozaki and T. Suyama, “Diastereoselective Conjugate Addition of 1-(α,β-unsaturated acyl)hydantoin with Nucleophiles,” Tetrahedron Letters, Vol. 46, No. 38, 2005, pp. 6411-6415. doi:10.1016/j.tetlet.2005.07.116
[4]	D. A. Evans, M. D. Ennis and D. J. Mathre, “Asymmetric Alkylation Reaction of Chiral Imide Enolate. A Practical Approach to the Enantioselective Synthesis of α-Substituted Carboxylic Acid Derivatives,” Journal of the American Chemical Society, Vol. 104, No. 6, 1982, pp. 1737- 1739. doi:10.1021/ja00370a050
[5]	K. Rück and H. Kunz, “Stereoselective Conjugate Addition of Organoaluminum Chloride to α,β-Unsaturated Carboxylic Acid Derivatives,” Synthesis, Vol. 1993, No. 10, 1993, pp. 1018-1028. doi:10.1055/s-1993-25990
[6]	M.-J. Wu, C.-C. Wu and P.-C. Lee, “Lewis Acid Promoted Asymmetric 1,4-Addition of Allyltrimethylsilane to Chiral α,β-Unsaturated N-Acylamides,” Tetrahedron Letters, Vol. 33, No. 18, 1992, pp. 2547-2548. doi:10.1016/S0040-4039(00)92238-X
[7]	J. R. Harding, R. A. Hughes, N. M. Kelly, A. Sutherland and C. L. Willis, “Synthesis of Isotopically Labelled L-aAmino Acid with an Asymmetric Centre at C-3”, Journal of the Chemical Society, Perkin Transactions 1, Vol. 2000, 2000, pp. 3406-3416. doi:10.1039/b005172l
[8]	S. M. Allin, M. S. Essat, C. H. Pita, R. D. Baird, V. McKee, M. Elsegood, M. Edgar, D. M. Andrews, P. Shah and I. Aspinall, “Applications of the Amino-Cope Rearrengement: Synthesis of Tetrahydropyran, d-Lactone and Piperidine Targets,” Organic & Biomolecular Chemistry, Vol. 3, 2005, pp. 809-815. doi:10.1039/b416179c