The Synthesis of Optically-Active erythro- Methylphenidate by Diastereoselective Hydrogenation Using Ru-BINAP Complex Catalyst

International Journal of Applied Chemistry
© 2020 by SSRG - IJAC Journal
Volume 7 Issue 2
Year of Publication : 2020
Authors : Yoshifumi Yuasa, Akiko Horizoe
pdf
How to Cite?

Yoshifumi Yuasa, Akiko Horizoe, "The Synthesis of Optically-Active erythro- Methylphenidate by Diastereoselective Hydrogenation Using Ru-BINAP Complex Catalyst," SSRG International Journal of Applied Chemistry, vol. 7,  no. 2, pp. 70-74, 2020. Crossref, https://doi.org/10.14445/23939133/IJAC-V7I2P110

Abstract:

Optically-active erythro-methylphenidate 1 has been synthesized from methyl 2-phenyl-2-(2’- piperidylidene)acetate 2 by diasteroselective hydrogenation using the Ru-BINAP complex catalyst as the key step. Piperidylidene acetate 2 was prepared by two routes either from 2,3,4,5-tetrahydro-6-methoxypyridine 4 or 5-Ncarbobenzyloxyamino-pentanoic acid 5.

Keywords:

Diasteroselective hydrogenation; methylphenidate, methyl 2-phenyl-2-(2’-piperidyl)-acetate, methyl 2-phenyl-2-(2’-piperidylidene)acetate, Ru-BINAP complex catalyst.

References:

[1] A. Shafi'ee, G. Hite. “The absolute configurations of the pheniramines, methylphenidates, and pipradrols” J. Med. Chem., 1969, 12, pp. 266-270.
[2] K. S. Partrick, R. W. Caldwell, R. M. Ferris, G. R. Breese. “Pharmacology of the enantiomers of threo- Methylphenidate” J. Pharmacol. Exp. Thr., 1987, 241, pp. 152-158.
[3] L. Szporny, P. Gorog. “Investigations into the correlations between monoamine oxidase inhibition and other effects due to methylphenidate and its stereoisomers” Biochem. Pharmacol., 1961, 8, pp. 263-268.
[4] R. Rometsch. “Process for the conversion of stereoisomers” U.S. Patent 2,957,880, 1960.
[5] A. Shafi'ee, S. Marathe, R. Bhatkar, G. Hite. “Absolute configurations of the enantiomeric pheniramines, methylphenidates, and pipradrols” J. Pharm.Sci., 1967, 56, pp. 1689-1690.
[6] D. L. Thai, M. T. Sapko, C. T. Reiter, D. E. Bierer, J. M. Perel. “Asymmetric synthesis and pharmacology of methylphenidate and its para-substituted derivatives” J. Med. Chem., 1998, 41, pp. 591-601.
[7] M. Prashad, H-Y, Kim, Y. Lu, Y. Liu, D. Har, O. Repic, T. J. Black, P. Ginnousis. “The first enantioselective synthesis of (2R,2’R)-threo-(+)-methylphenidate hydrochloride” J. Org. Chem., 1999, 64, pp. 1750 - 1753.
[8] J. M. Axten, R. Ivy, L. J. Krim, D. Winkler. “An enantioselective synthesis of d-threo-methylphenidate” J. Am. Chem. Soc., 1999, 121, pp. 6511-6512.
[9] Y. Matsumura, Y. Kanda, K. Shirai, O. Onomura, T. Maki. “A convenient method for synthesis of optically active methylphenidate from N-methoxycarbonylpiperidine by utilizing electrochemical oxidation” Org. Lett., 1999, 1, pp. 175-178.
[10] Y. Matsumura, Y. Kanda, K. Shirai, O. Onomura, T. Maki. “Convenient method for synthesis of optically active methylphenidate from N-methoxycarbonylpiperidine by utilizing electrochemical oxidation and Evans aldol-type Reaction” Tetrahedron, 2000, 56, pp. 7411-7422.
[11] M. Prashad, Y. Liu, H-Y. Kim, Y. Lu, O. Repic, T. J. Black.“Enantioselective synthesis of (2S,2’R)-erythreo-Methyl-phenidate” Tetrahedron: Asymmetry, 1999, 10, pp. 3479 - 3482.
[12] L. Chunzheng, J. Yuanbo, C. Qing, L. Jianqi, L. Bonan. “Concise and facile synthesis of (R,R)-dexmethylphenidate hydrochloride and its three stereoisomers” Synthetic Communications, 2017, 47, pp. 1301-1306.
[13] L. Xing, C. Shen, Y. Sun, L. Huang, Y. Zheng, J. Li. “An improved and efficient process for the production of highly pure dexmethylphenidate hydrochloride” Journal of Heterocyclic Chemistry, 2017, 54, pp. 1298-1303.
[14] G. Stephen, A. Davies, M. Fletcher, E. Matthew, M. Peters, M. Paul, J. Roberts, E. Thomson. “The asymmetric synthesis of (S,S)-methylphenidate hydrochloride via ringopening of an enantiopure aziridinium intermediate with phenylmagnesium bromide” Tetrahedron, 2019, 75 , 130713.[15] K. E. Koenig. In Asymmetric synthesis. Vol. 5. Edited by Morrison, J. D., Academic Press, New York. 1985, pp.71-101.
[16] R. Noyori, H. Takaya. “BINAP: An efficient chiral element for asymmetric catalysis” Acc. Chem. Res.,1990, 23, pp. 345-350.
[17] H. Takaya, R. Noyori. In Comprehensive Organic Synthesis.Vol. 8. Edited by Trost, B. M., Fleming, I., Pergamon Press, Oxford. 1991, Chap. 3.2. p.433-469.
[18] R. Noyori. “Asymmetric Catalysis by Chiral Metal Complexes” CHEMTECH, 1992, pp. 360-367.
[19] H. Takaya, T. Ohta, R. Noyori. “In Catalytic Asymmetric Synthesis” Edited by Ojima, I. VCH Publishers, New York. 1993.
[20] R. Noyori. “In Asymmetric Catalysis in Organic Synthesis” John Wiley & Sons, Inc. New York., 1994, Chap. 2.
[21] R. Noyori. “Organometallic ways for the multiplication of chirality” Tetrahedron, 1994, 50, pp. 4259-4292
[22] W. Tang, X. Zhang. “New chiral phosphorus ligands for enantioselective hydrogenation” Chem. Rev., 2003, 103, pp. 3029-3070, and reference cited therein.
[23] T. Ikariya, Y. Ishii, H. Kawano, T. Arai, M. Yoshikawa, S. Akutagawa. “Synthesis of novel chiral ruthenium complexes of 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl and their use as asymmetric catalysts” J. Chem. Soc., Chem. Commun., 1985, pp. 922-924.
[24] K. Bhandari, V. Virmani, V. A.Murti, P. C. Jain, N. Anand.“Chemistry of lactim ethers: Part II. Reactions with amines and carbanions” Indian J. Chem (B), 1979, 17B, pp. 104-106.
[25] A. E. Wick, P. A. Bartlett, D. Dolphin. “The total synthesis of ipalbidine and ipalbine” Helv. Chem. Acta., 1971, 54, pp. 513-522.
[26] S. Peterson, E. Tietze. “Reaktionen Cyclischer Lactimäther mit acylierten hydrazin derivaten” Chem. Ber., 1957, 90, pp. 909-921.
[27] B. D. Harris, K. L. Bhat, M. M. Jonllie. “Synthetic study of didemnins. II. Approaches to statine diastereomers” Tetrahedron Lett., 1987, 28, pp. 2837-2840.
[28] T. Ohta, Y. Tonomura, K. Nozaki, H. Takaya, K. Mashima. “An Anionic DinuclearBINAP−Ruthenium(II) Complex: Crystal structure of [NH2Et2]{RuCl((R)-p-tolyl-BINAP)}2(μ-Cl)3] and its use in asymmetric Hydrogenation” Organometallics, 1996, 15, pp. 1521-1523.