Stereoselective Reduction of Amino Ketone with Sodium Borohydride in the Presence of Metal Chloride. A Simple Pathway to S-Propranolol
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.
[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
[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
@article{"International Journal of Chemical, Materials and Biomolecular Sciences:61511", author = "R. Inkum and A. Teerawutgulrag and P. Puangsombat and N. Rakariyatham", title = "Stereoselective Reduction of Amino Ketone with Sodium Borohydride in the Presence of Metal Chloride. A Simple Pathway to S-Propranolol", 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", volume = "6", number = "7", pages = "604-4", }
