Stereoselective method for synthesizing dolaphenine

Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...

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548204, C07D27720

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060204958

ABSTRACT:
The present invention relates to a method for the stereospecific synthesis of an enantiomer of a chiral amine, wherein the chiral amine has the formula R.sup.1 CH(NH.sub.2)R.sup.2. R.sup.1 and R.sup.2 are each independently selected from the group consisting of alkyl, aryl and heterocyclic and radicals. This method is particularly useful for stereospecifically synthesizing S-dolaphenine. The method involves contacting a chiral enantiomer of norephedrine with borane, within an aprotic solvent to form a complex for stereospecifically reducing oximes. The complex is then contacted with an oxime, thereby stereospecifically reducing said oxime to form an enantiomer of a chiral amine.

REFERENCES:
patent: 4978744 (1990-12-01), Pettit et al.
patent: 5200561 (1993-04-01), Konya et al.
Pettit, G. R., et al., "The Absolute Configuration and Synthesis of Natural (-)-Dolastatin 10," J. Am. Chem. Soc., 111: 5463-5465 (1989).
Irako, N., et al., "A New Efficient Synthesis of (S)-Dolaphenine ((S)-2-Phenyl-l-(2-thiazolyl)ethylamine), the C-Terminal Unit of Dolastatin 10," Tetrahedron, 48(35): 7251-7264 (1992).
Shioiri, T., et al., "Stereoselective Synthesis of Dolastatin 10 and Its Congeners," Tetrahedron, 49(9): 1913-1924 (1993).
Pettit, G. R., et al., "Structure of the Cyclic Peptide Dolastatin 3 from Dolabella auricularia," J. Am. Chem. Soc., 104(3): 905-907 (1982).
Brendenkamp, M. W., et al., "Observations of the Hantzsch Reaction: Synthesis of N-.sup.t BOC-S-Dolaphenine," Synthetic Communications, 22(21): 3029-3039 (1992).
Fujita, M., et al., "Reduction of Oximes with Hydrosilame/H.sup.+ Reagent," Chemistry Letters, pp. 837-838 (1986).
Hamada, Y., et al., "New Methods and Reagents in Organic Synthesis. 67. A General Synthesis of Derivatives of Optically Pure 2-(1-Aminoalkyl)thiazole-4-carboxylic Acids," J. Org. Chem., 52: 1252-1255 (1987).
Pettit, G.R., et al., "The Dolastatins 16, Synthesis of Dolaphenine," Heterocycles, 39(1): 81-100 (1994).
Brown, H.C. and Krishnamurthy, S., "Boranes for Organic Reductions--A Forty Year Odyssey," Aldrichimica Acta, 12(1): 167-175 (1979).
S. Itsuno, et al., "Asymmetric Synthesis Using Chirally Modified Borohydrides, Part 3. Enantioselective Reduction of Ketones and Oxime Ethers with Reagents Prepared from Borane and Chiral Amino Alcohols," J. Chem. Soc. Perkin Trans., 1: 2039-2044 (1985).
Y. Komeyoshi, "Chiral Hydroxyphenethylamine Complexes with Borane Derivatives," Chemical Abstracts, 105: 114714c 642-643 (1986).
Sakito, Y., et al., "Asymmetric Reduction of Oxime Ethers. Distinction of Anti and Syn Isomers Leading to Enantiomeric Amines," Tetrahedron Letters, 29(2): 223-224 (1988).
Dondoni, A. and Merino, P., "Chemistry of the Enolates of 2-Acetylthiazole: Aldol Reactions with Chiral Aldehydes to Give 3-Deoxy Aldos-2-uloses and 3-Deoxy 2-Ulosonic Acids. A Short Total Synthesis of 3-Deoxy-D-manno-2-octulosonic Acid (KDO)," J. Org. Chem., 56: 5294-5301 (1991).
Welch, W.M., et al., "Nontricyclic Antidepressant Agents Derived from cis- and trans-1-Amino-4-aryltetralins," J. Med. Chem., 27: 1508-1515 (1984).
Noyori, R., et al., "Rational Designing of Efficient Chiral Reducing Agents. Highly Enantioselective Reduction of Aromatic Ketones by Binaphthol-Modified Lithium Aluminum Hydride Reagents," J. Am. Chem. Soc., 106: 6709-6716 (1984).
B.o slashed.ges.o slashed., K.P., et al., "3-Phenyl-1-indanamines. Potential Antidepressant Activity and Potent Inhibition of Dopamine, Norepinephrine, and Serotonin Uptake," J. Med. Chem., 28: 1817-1828 (1985).
Schmidt, U., et al., "Synthesis of Optically Active 2-(10Hydroxyalkyl)-thiazole-4-carboxylic Acids and 2-(1-Aminoalkyl)-thiazole-4-carboxylic Acids," Synthesis, pp. 992-998 (Dec. 1986).
Sakane, H., et al., "Preparation of dimethoxydeoxybenzoin oxime derivatives as intermediates for optically active 1,2-bis(4-methoxyphenyl)ethylamine," (from Chemical Abstracts, 1994, 120, Abstract No. 191318). (This abstract corresponds to reference AN, Japanese Patent No. 05,279,311).
Sakane, H. and Suzukamo, T., "Preparation of optically active oxazaborolidines as asymmetric reducing agents," (from Chemical Abstracts, 1995, 123, Abstract No. 56272). (This abstract corresponds to reference AN, Japanese Patent No. 06,340,674).
Janot, et al., "(3.alpha.,5.alpha.)-3-Aminopregnan-20-one; 3.alpha.-amino-20-oxo-5.alpha.-pregnane," Compt. Rend., 246: 3076(1958). (From The Merck Index, 12th Ed., 1996, Abstract No. 4314. Funtumine.).
Fouche, J.C. and Gueremy, C.G.A., "10,11-Dihydro-N, 5-dimetyl-5H-dibenz[b,flazepin-10-amine; 10,11-dihydro-5-methyl-10-(methylamino)-5H-dibenz[b,flazepine," S. Afr. pat. 68 00345 corresp to U.S. pat. 3,622,565 (1968/1971). (From The Merck Index, 12th Ed., 1996, Abstract No. 5991. Metapramine.).

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