Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
1998-12-29
2001-07-03
Berch, Mark L. (Department: 1611)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C540S205000, C540S229000, C540S230000, C540S301000, C540S302000, C540S310000, C540S347000, C540S507000, C540S518000, C540S526000, C540S533000, C546S137000, C546S142000, C546S155000, C546S183000, C546S243000, C548S485000, C548S513000, C548S544000
Reexamination Certificate
active
06255479
ABSTRACT:
BACKGROUND OF THE INVENTION
&agr;-Oxolactams are useful synthons for preparing a variety of natural products and biologically active compounds (for example see A. Hisham
Tetrahedron,
1997, 53, no. 5, 1813-1822). They can also be used to prepare synthetically useful &agr;-substituted-&ohgr;-amino carboxilic acids, and to prepare a variety of isoindigoide dyes (G. Kollenz, et al.
Tetrahedron,
1996, 52, no. 15, 5427-5440).
&agr;-Oxo-&bgr;-lactams, such as 6-oxopenams, 7-oxocephems and 6-oxopenems, are also useful for preparing &agr;-alkylidene-&bgr;-lactams and &agr;-vinylidene-&bgr;-lactams, both important classes of &bgr;-lactamase inhibitors (U.S. Pat. No. 5,597,817, issued Jan. 29, 1997 (“817”); U.S. Pat. No. 5,629,306, issued May 13, 1997 (“306”); Buynak et al.,
J. Org. Chem.,
1993, 58, 1325.; Buynak et al.,
J. Am. Chem. Soc.,
1994, 116, 10955; Buynak et al.,
J. Med. Chem.,
1995, 38, 1022; Buynak et al.,
Bioorg. Med. Chem. Lett.,
1995, 5, 1513; Arisawa et al.,
J. Antibiot.,
1982, 35, 1578; Brenner et al.,
Biochemistry,
1984, 23, 5839; Chen et al.,
Tetrahedron Lett.,
1986, 27, 3449; Bennet et al.,
J. Antibiot.,
1991, 44, 969.
&agr;-Oxo-&bgr;-lactams have also been used to prepare cytotoxic analogs of paclitaxel (J. Kant et al.
Tetrahedron Letters,
1996, 37, 6495-6498); and to prepare &agr;-aminoacid N-carboxy anhydrides and their corresponding &agr;-amino acid derivatives (C. Palomo
J. Org. Chem.,
1994, 59, 3123-3130).
J. M. van der Veen et al.
J. Org. Chem.,
1989, 54, 5758-5762 disclose the preparation of specific &agr;-oxo-&bgr;-lactams by hydrolysis of the corresponding &agr;-chloro-&agr;-phenylthio-&bgr;-lactams, which are prepared by the treatment of &agr;-phenylthio-&bgr;-lactams with N-chlorosuccinimide. C. Palomo et al.
J. Org. Chem,
1994, 59, 3123-3130, disclose the preparation of specific &agr;-oxo-&bgr;-lactams by oxidation of the corresponding &agr;-hydroxy-&bgr;-lactams using Me
2
SBr
2
—NEt
3
, CrO
3
— pyridine, or DMSO-P
2
O
5
. U.S. patents '817 and '306 disclose the preparation of specific &agr;-oxo-&bgr;-lactams by treatment of the corresponding &agr;-amino-&bgr;-lactams with trifluoromethanesulfonic anhydride and triethylamine, followed by aqueous acid.
Existing methods for preparing &agr;-oxolactams are limited because they require the use of toxic or corrosive reagents, produce hazardous side products, require starting materials that are difficult or expensive to prepare, or yield products that can not be easily isolated or purified. Additionally, existing methods can not conveniently be preformed to yield products on a commercially useful (e.g. kilogram) scale. Therefore, there is a need for improved methods for preparing &agr;-oxolactams, which overcome one or more of the limitations of the existing synthetic methods.
SUMMARY OF THE INVENTION
The present invention provides a method comprising reacting an &agr;-diazolactam with an oxygen donor, in the presence of a transition metal catalyst to yield the corresponding &agr;-oxolactam. The method utilizes non-toxic reagents, does not produce hazardous side products, and yields a product that can be easily isolated. Additionally, the method is mild and selective, and allows for the preparation of the &agr;-oxolactam functionality in the presence of a wide variety of other functional groups.
The method may also further comprise the step of preparing the &agr;-diazolactam from a corresponding &agr;-aminolactam by diazotization.
REFERENCES:
patent: 4456755 (1984-06-01), Sheehan
patent: 5597817 (1997-01-01), Buynak et al.
patent: 5629306 (1997-05-01), Buynak et al.
patent: 5681563 (1997-10-01), Buynak et al.
patent: 5760027 (1998-06-01), Buynak et al.
patent: 2708219 (1977-09-01), None
patent: 0 050 805 (1982-05-01), None
patent: 0 150 984 (1985-08-01), None
patent: 0 367 606 (1990-05-01), None
patent: 0 043 546 (1992-01-01), None
patent: 98/24793 (1998-06-01), None
Abd El-Nabi, H.A., “Novel Heterocycles: A convenient Synthesis of Pyrrolo [2,3-d]pyrazole; Cycloaddition reation of N-aryl(methyl)pyrrol-2,3-Diones to diazomethane and olefins”,Tetrahedron, 53(5), 1813-1822, (Feb. 1997).
Arisawa, M., et al., “6-Acetylmethylenepenicillanic Acid (Ro 15-1903), A Potent &bgr;-Lactamase Inhibitor. I. Inhibition of Chromosomally and R-Factor-Mediated &bgr;-Lactamases”,The Journal of Antibiotics, 35(11), 1578-1583, (Nov. 1982).
Bennett, I.S., et al., “6-(Substituted Methylene) Penems, Potent Broad Spectrum Inhibitors of Bacterial &bgr;-Lactamase. V. Chiral 1,2,3-Triazolyl Derivatives”,The Journal of Antibiotics, 44(9), 969-978, (Sep. 1991).
Brenner, D.G., et al., “6-(Methoxymethylene) penicillanic Acid: Inactivator of RTEM &bgr;-Lactamase fromEscherichia coli”,Biochemistry, 23(24), 5839-5846, (Nov. 20, 1984).
Buynak, J.D., et al., “Synthesis and biological activity of 7-alkylidenecephems”,J. Med. Chem., 38, 1022-1034, (1995).
Buynak, J.D., et al., “Synthesis and mechanistic evaluation of 7-vinylidenecephem sulfones as &bgr;-lactamase inhibitors”,J. of Am. Chem. Soc., 116, 10955-10965, (1994).
Buynak, J.D., et al., “Synthesis of 6-vinylidenepenams”,The Journal of Organic Chemistry, 58(6), 1325-1335, (Mar. 12, 1993).
Buynak, J.D., et al., “The Synthesis and Lactamase Inhibotory Activity of 6-(Carboxymethylene) Pencillins and 7-(Carboxymethylene) Cephalosporins”,Bioorganic & Medicinal Chemistry Letters, 5 (14), 1513-1518, (1995).
Chen, Y.L., et al., “Synthesis of a Potent &bgr;-Lactamase Inhibitor-1,1-Dioxo-6-(2-Pyridyl) Methylenepenicillanic Acid and its Reaction with Sodium methoxide”,Tetrahedron Letters, 27 (30), 3449-3452, (1986).
Hagiwara, D., et al., “An Efficient Synthesis of 6-Oxopenicillanic and 7-Oxocephalosporanic Acid Derivatives”,Journal of the Chemical Society Chemical Communications, 11, 578-579, (Jun. 1, 1982).
Kant, J., et al., “Diastereoselective Addition of Grignard Reagents to Azetidine-2,3-dione: Synthesis of Novel Taxol Analogues”,Tetrahedron Letters, 37 (36), 6495-6498, (Sep. 2, 1996).
Kollenz, G., et al., “Reactions of Cyclic Oxalyl Compounds—38. New Isoindigoide Dyes from Heterocyclic 2,3-Diones—Synthesis and Thermal Rearrangement”,Tetrahedron, 52(15), 5427-5440, (Apr. 1996).
Martin, M.G., et al., “Epoxides as Alkene Protecting Groups. A Mild and Efficient Deoxygenation”,Tetrahedron Letters, 25 (3), 251-254, (1984).
Palomo, C., et al., “New Synthesis of &agr;-Amino Acid N-Carboxy Anhydrides through Baeyer-Villiger Oxidation of &agr;-keto &bgr;-Lactams”,The Journal of Organic Chemistry, 59 (11), 3123-3130, (Jun. 3, 1994).
van der Veen, J.M., et al., “Synthesis of Azetidine-2,3-diones (&agr;-Keto &bgr;-Lactams) via 3-(Phenylthio)-2-azetidinones”,The Journal of Organic Chemistry, 54 (24), 5758-5762, (Nov. 24, 1989).
Ursini, F., et al., “New Synthesis of 6-Oxopenicillanates by Ozonolysis of 6-Diazopenicillanates”,Synthesis, 4, 363-364, (1992).
Buynak John D.
Rao Akireddy Srinivasa
Berch Mark L.
Research Corporation Technologies Inc.
Schwegman Lundberg Woessner & Kluth P.A.
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