Stereoselective Reduction of Amino Ketone with Sodium Borohydride in the Presence of Metal Chloride. A Simple Pathway to S-Propranolol

Authors: R. Inkum, A. Teerawutgulrag, P. Puangsombat, N. Rakariyatham

Abstract:

Propranolol is worldwide hypertension drug that is active in S-isomer. Patients must use this drug throughout their lives, and this action employsa significant level of expenditure. A simpler synthesis and lower cost can reduce the price for the patient. A sis pathway of S-propranolol starting from protection of (R,S)-propranolol with di-t-butyldicarbonate and then the product is oxidized with pyridiniumchlorochromate. The selective reduction of ketone occurrs with sodiumborohydride in the presence of metal chloride provided S-propranolol.

Keywords: S-propranolol, selective reduction, sodium borohydride, metal chloride

Digital Object Identifier (DOI): doi.org/10.5281/zenodo.1079292

References:

[1] T. Seki, T. Takezaki, R. Ohuchi, H. Ohuyabu, T. Ishimori, and K. Yasuda, "Studies on agents with vasodilator and ¶Çêò-blocking activities I", Chemical& Pharmaceutical Bulletin., 42, 1994, pp. 1609-1616.
[2] T. Fujioka, S. Teramoto, and T. Mori, "Novel positive inotropic agents: synthesis and biological activities of 6-(3-amino-2-hydroxypropoxy)- 2(1H)-quinolinone derivatives", J. Med. Chem., 35, 1992, pp. 3607-3612.
[3] A. M. Barrett, and V. A. Cullum, "The biological properties of the optical isomers of propranolol and their effects on cardiac arrhythmias", Br. J. Pharmacol., 34, 1968, pp. 43-55.
[4] R. Howe, and R. G. Shanks, "Optical isomers of propranolol", Nature , 210, 1966, pp. 1336-1338.
[5] K. H. Rahn, A. Hawlina, F. Kersting, and G. Planz, "Studies on the antihypertensive action of the optical isomers of propranolol in man", Naunyn Schmiedebergs Arch. Pharmacol., 286, 1974, pp. 319-323.
[6] T. Walle, U. K. Walle, M. J. Wilson, T. C. Fagan, and T. E.Gaffney, "Stereoselective ring oxidation of propranolol in man", Br. J. Chin. Pharmacol., 18, 1984, pp. 741-748.
[7] (a) M. Noritada, and O. Nobuo, "Preparation of optically active 1- acetoxy-2-aryloxypronitrile and its application to a facile synthesis (S)-(- )-propranolol", TetLett., 26, 1985, pp. 5533-5534. (b) H. S. Bevinakatii, and A. A. Banerji, "Practical chemoenzymatic synthesis of both enantiomers of propranolol", J. Org. Chem., 56, 1991, pp. 5372-5375.(c) H. S. Bevinakatii, and A. A. Banerji, "Lipase catalysis in organic solvents. Application to the synthesis of (R)- and (S)-atenolol", J. Org. Chem., 57, 1992, pp. 6003-6005.
[8] H. Takahashi, S. Sakuraba, H. Takeda, and K. Achiwa, "Asymmetric reaction catalyzed by chiral metal complexes. 41. Highly efficient asymmetric hydrogenation of amino ketone derivatives leading to practical syntheses of (S)-propranolol and related compounds", J.Am. Chem. Soc., 112, 1990, pp. 5876-5878.
[9] J. M. Klunder, S. Y. Ko, and K. B. Sharpless, "Asymmetric epoxidation of allyl alcohol: Efficient routes to homochiral ¶Çêò-adrenergic blocking agents", J. Org. Chem., 51, 1986, pp. 3710-3712.
[10] R. A. Veloo, and G. J. Koomen, "Synthesis of enantiomerically pure (S)- (-)-propranolol from sorbitol", TettAsym., 4, 1993, pp. 2401-2404