Organic compounds -- part of the class 532-570 series – Organic compounds – Halogen containing
Reexamination Certificate
2005-08-26
2008-12-16
Marx, Irene (Department: 1651)
Organic compounds -- part of the class 532-570 series
Organic compounds
Halogen containing
C570S182000, C570S190000, C435S280000
Reexamination Certificate
active
07465842
ABSTRACT:
The invention relates to biocatalytic methods for preparing enantiomerically pure stereoisomers of 1-(2,6-dichloro-3-fluorophenyl)ethanol. Disclosed are methods of preparation of the desired (S)-enantiomer, which methods are based on a combination of enzymatic resolution, chemical esterification and chemical hydrolysis with inversion of 1-(2,6-dichloro-3-fluorophenyl)ethyl esters or stereoselective bio-reduction of 2,6-dichloro-3-fluoro-acetophenone with a biocatalyst such as an enzyme or a microorganism. The chiral (S)-enantiomer can be used in the synthesis of certain enantiomerically enriched, ether linked 2-aminopyridine compounds that potently inhibit auto-phosphorylation of human heptocyte growth factor receptor.
REFERENCES:
patent: 5310666 (1994-05-01), Aretz et al.
patent: 5391495 (1995-02-01), Patel et al.
patent: 5457052 (1995-10-01), Tsuboi et al.
patent: 5928933 (1999-07-01), Dicosimo et al.
patent: 6451587 (2002-09-01), Burns et al.
patent: 6515134 (2003-02-01), Amano et al.
patent: 6638758 (2003-10-01), Hansen et al.
patent: 6642387 (2003-11-01), Amano et al.
patent: 6703396 (2004-03-01), Liotta et al.
patent: 6800477 (2004-10-01), Patel et al.
patent: 7230098 (2007-06-01), Cui et al.
patent: 2005/0009840 (2005-01-01), Cui et al.
patent: WO 02/077258 (2002-10-01), None
patent: WO 03/093477 (2003-11-01), None
Adolph, H., et al., “Structural Basis For Substrate Specificity Differences Of Horse Liver Alcohol Dehydrogeanse Isozymes,”Biochemistry, 2000, 12885-12897, vol. 39.
Allenmark, S., et al., “Chiral Liquid Chromatographic Monitoring Of Asymmetric Carbonyl Reduction By Some Yeast organisms,”Enzyme Microbial Technol., 1989, 177-179, vol. 11.
Almsick, A., et al., “Enzymatic Preparation Of Optically Active Cyanohydrin Acetates,”J. Chem. Soc. Chem. Commun., 1989, 1391-1393, vol. 18.
Barbieri, C., et al., “Chemo-Enzymatic Synthesis of (R) And (S)-3,4-Dichlorophenylbutanolide Intermediate In The Synthesis Of Sertraline,”Tetrahedron: Asymmetry, 1999, 3931-3937, vol. 10.
Bauer, A., et al., “Polyvinyl Alcohol-Immobilized Whole-Cell Preparations for The Biotransformation Of Nitriles,”Biotechnology Letters, 1996, 343-348, vol. 18, No. 3.
Bouzemi, N., et al., “On The Use Of Succinic Anhydride As Acylating Agent For Practical Resolution Of Aryl-Alkyl Alcohols Through Lipase-Catalyzed Acylation,” Tetrahedron Letters, 2004, 627-630.
Choi, J., et al., “Aminocyclopentadienyl Ruthenium Complexes As Racemization Catalysts For Dynamic Kinetic Resolution Of Secondary Alcohols At Ambient Temperature,”J. Org. Chem., 2004, 1972-1977, vol. 69.
Corey, E., et al., “A Stable And Easily Prepared Catalyst For The Enantioselective Reduction Of Ketones. Applications To Multistep Syntheses,”J. Am. Chem. Soc., 1987, 7925-7926, vol. 109.
D'Arrigo, P., et al., “The Effect Of Absorbing Resins On Substrate Concentration And Enantiomeric Excess In Yeast Reduction,”Tetrahedron: Asymmetry, 1997, 2375-2379, vol. 8, No. 14.
Dale, J., et al., “Nuclear Magnetic Resonance Enantiomer Reagents. Configurational Correlations via Nuclear Magnetic Resonance Chemical Shifts Of Diastereomeric Mandelate,O-Methylmandelate, And αMethoxy- α-Trifluoromethylphenylacetate (MTPA) Esters,”Journal Of The American Chemical Society, 1973, 512-519, vol. 95, No. 2.
Danda, H., et al., “Preparation Of Optically Active Secondary Alcohols By Combination Of Enzymatic Hydrolysis And chemical Transformation ,”Tetrahedron, 1991, 8701-8716, vol. 47, No. 41.
Dijksman, A., et al., “Efficient Ruthenium-Catalyzed Racemization Of Secondary alcohols: Application To Dynamic Kinetic Resolution,”Tetrahedron: Asymmetry, 2002, 879-884, vol. 13.
Gotor, V. “Enzymes In Organic solvents: The Use Of Lipases And (R)-Oxynitrilase For the Preparation Of Products Of Biological Interest,”Molecules, 2000, 290-292, vol. 5.
Grunwald, J., et al., “Asymmetric Oxidoreductions Catalyzed By Alcohol Dehydrogenase In Organic Solvents,I”J. Am. Chem. Soc., 1986, 6732-6734, vol. 108.
Itoh, N., et al., “Chiral Alcohol Production By NADH—Dependent Phenylacetaldehyde Reductase Coupled With in situ Regeneration of NADH,”Euro. J. Biochem., 2002, 2394-2402, vol. 269.
Jiang, B., et al., “Highly Enantioselective Reduction Of Achiral Ketones With NaBH4/Me3SiC1 Catalyzed By (S)-α, α-Diphenylpyrrolidinemethanol,”Tetrahedron Letters, 2000, 10281-10283, vol. 41.
Johansson, A., et al., “Horse Liver Alcohol Dehydrogenase Can Accept NADP+As Coenzyme In High Concentrations Of Acetonitrile,”Eur. J. Biochem., 1995, 551-555, vol. 227.
Kim, M., et al., “(S)-Selective Dynamic Kinetic Resolution Of Secondary Alcohols By The Combination Of Subtilisin And An Aminocyclopentadienylruthenium Complex As The Catalysts,”J. Am. Chem. Soc., 2003, 11494-11495, vol. 125.
Kirihara, M., et al., “Synthesis Of Optically Active 2,2-Difluorohomoallylalcohols By Lipase-Catalyzed Transesterification,”Tetrahedron: Asymmetry, 2002, 2283-2289, vol. 13.
Liu, H., et al., “Enantiopure Building Blocks For Chiral Drugs From Racemic Mixtures Of Secondary Alcohols By Combination Of Lipase Catalysis And Mitsunobu Esterification,”Chirality, 2002, 25-27, vol. 14.
Mathre, D., et al., “A Practical Process For The Preparation Of Tetrahydro-1-methyl-3,3-diphenyl-1H,3H-pyrrolo[l,2-c]-[1,3,2]oxazaborole-Borane. A Highly Enantioselective Stoichiometrict And Catalytic Reducing Agent,”J. Org. Chem., 1983, 2880-2888, vol. 58.
Mitsunobu, O. “The Use Of Diethyl Azodicarboxylate AndTriphenylphosphine In Synthesis And Transformation Of Natural Products,”Synthesis, 1981, 1-28.
Mukaiyama, T., et al., Optical Interconversion Of Enantiomeric Secondary Alcohols Using 2-Flurobenzothiazolium Salt,Chemistry Letters, 1976, 893-896.
Naemura, K., et al., “Enantioselective Acylation Of Primary And Secondary Alcohols Catalyzed By Lipase QL FromAlcaligenessp.: A Predictive Active Site Model For Lipase QL To Identify Which Enantiomer Of An Alcohol Reacts Faster In This Acylation,”Tetrahedron: Asymmetry, 1996, 3285-3294, vol. 7, No. 11.
Naemura, K., et al., “Lipase-Catalyzed Enantioselective Acylation Of Alcohols: A Predictive Active Site Model For Lipase YS To Identify Which Enantiomer Of An alcohol Reacts Faster In This Acylation,”Tetrahedron: Asymmetry, 1995, 2385-2394, vol. 6, No. 9.
Nakamura, K., et al., “Asymmetric Reduction Of Ketones By The Acetone Powder OfGeotrichum Candidum,” Tetrahedron Letters, 1996, 1629-1632, vol. 37, No. 10.
Nakamura, K., et al., “Asymmetric Reduction Of Ketones By The Acetone Powder OfGeotrichum Candidum,” J. Org. Chem, 1998, 8957-8964, vol. 63.
Nakamura, K., et al., “Recent Developments In Asymmetric Reduction Of Ketones With Biocatalysts,”Tetrahedron: Asymmetry, 2003, 2659-2681, vol. 14.
Pai, Y., et al., “Resolution Of Homoallylic Alcohols Containing Dithioketene Acetal Functionalities. Synthesis Of Optically Active y-Lactones By A Combination Of Chemical And Enzymatic Methods,”J. Org. Chem., 1994, 6018-6025, vol. 59.
Patel, R., et al., “Oxidation Of Secondary Alcohols To Methyl Ketones By Yeasts,”Appied. Environmental Microbiology, 1979, 219-223, vol. 38, No. 2.
Ponpipom, M., et al., “Enantioselective Cyclization Of Chiral Butane-1,4-Diols To Chiral Tetrahydrofurans: Synthesis Of Chiral Trans-2-(3-Methoxy-5-Methysulfonyl-4-Propoxyphenyl)-5-(3,4,5-Trimethoxyphenyl) Tetrahydrofuran (L-659,989), A Potent Paf-Receptor Antagonist,”Tetrahedron Letters, 1988, 6211-6214, vol. 29, No. 48.
Prelog, V., et al., “Specification Of The Stereospecificity Of Some Oxido-Reductases By Diamond Lattice Sections,”Pure and Applied Chemistry, 1964, 119-130, vol. 9, Butterworths, London.
Rotthause, O., et al., “Efficient cyclization Of Squalene Epoxide To Lanosterol With Immobiliz
Kung Pei-Pei
Martinez Carlos
Tao Junhua
Agouron Pharmaceuticals , Inc.
Hanley Susan
Marx Irene
Yakovleva Galina M.
Zielinski Bryan C.
LandOfFree
Enantioselective biotransformation for preparation of... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Enantioselective biotransformation for preparation of..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Enantioselective biotransformation for preparation of... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-4037075