Organic compounds -- part of the class 532-570 series – Organic compounds – Unsubstituted hydrocarbyl chain between the ring and the -c-...
Reexamination Certificate
2005-03-15
2005-03-15
Raymond, Richard L. (Department: 1624)
Organic compounds -- part of the class 532-570 series
Organic compounds
Unsubstituted hydrocarbyl chain between the ring and the -c-...
C540S490000, C540S492000, C540S500000, C540S501000, C540S502000, C540S503000, C544S002000, C544S007000, C544S008000, C544S065000, C544S066000, C544S180000, C544S265000, C544S298000, C548S100000, C548S122000, C548S124000, C548S127000, C548S250000, C548S300100, C548S304400, C548S356100, C548S361100, C548S440000, C548S469000, C568S001000, C568S012000, C568S013000
Reexamination Certificate
active
06867298
ABSTRACT:
The present invention relates to copper-catalyzed carbon-heteroatom and carbon-carbon bond-forming methods. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of an amide or amine moiety and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In additional embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between a nitrogen atom of an acyl hydrazine and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In other embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of a nitrogen-containing heteroaromatic, e.g., indole, pyrazole, and indazole, and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-oxygen bond between the oxygen atom of an alcohol and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. The present invention also relates to copper-catalyzed methods of forming a carbon-carbon bond between a reactant comprising a nucleophilic carbon atom, e.g., an enolate or malonate anion, and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. Importantly, all the methods of the present invention are relatively inexpensive to practice due to the low cost of the copper comprised by the catalysts.
REFERENCES:
patent: 2490813 (1949-12-01), Hughes et al.
patent: 4259519 (1981-03-01), Stille
patent: 4423234 (1983-12-01), Plummer et al.
patent: 4642374 (1987-02-01), Lucy et al.
patent: 4659803 (1987-04-01), Bartmann et al.
patent: 4734521 (1988-03-01), Frazier
patent: 4764625 (1988-08-01), Turner et al.
patent: 4983774 (1991-01-01), Cahiez et al.
patent: 5159115 (1992-10-01), Pappas et al.
patent: 5300675 (1994-04-01), Elango
patent: 5405981 (1995-04-01), Lipshutz
patent: 5705697 (1998-01-01), Goodbrand et al.
patent: 5808055 (1998-09-01), Nakajima et al.
patent: 5908939 (1999-06-01), Baak et al.
patent: 6180836 (2001-01-01), Cheng et al.
patent: 6541639 (2003-04-01), Zhou et al.
patent: 20020010347 (2002-01-01), Werner et al.
patent: 2148613 (2000-05-01), None
Beletskaya et al, “Pd- and Cu-catalyzed selective Arylation of Benzotriazole” Tetrahedron Letters, vol. 39, pp. 5617-5620 (1989).*
Kiyomori et al, “An Efficient Copper-Catalyzed Coupling of Aryl Halides with Imidazoles” Tetrahedron Letters, vol. 40, pp. 2657-2660 (1999).*
U.S. Appl. No. 60/220932, filed Jul. 2000, Domestic Priority U.S. Appl. No. 6,541,639.*
Faith, Keyes, and Clark's Industrial Chemicals, 4thed., pp. 674-678, John Wiley & Sons (1975).
Kondratov and Shein, “Nucleophilic Substitution in the Aromatic Series.L.V. Reaction of O-Nitrochlorobenzene with Ammonia in the Presence of Copper Compounds”, Zhumal Organicheskoi Khimii, vol. 15(11): 2387-2390 (1979) (as abstracted by CAPLVS).
Vainshtein and Tomilenko; “Exchange of Halogens in Halobenzenes in a Reaction with Ammonia with Participation of Copper”, Zhumal Vsesoyuznogo Khimicheskogo Obshchestva im. D. I. Mendeleeva, 13 (6): 709-710, (1968) (as abstracted by CAPLVS).
Arai et al; “The Ullmann Condensation Reaction of Haloanthraquinone Derivatives With Amines in Aprotic Solvents. IV. Kinetic Studies of the Condensation with Ethylenediamine”,Bulletin of the Chemical Society of Japan 52(6): 1731-1734, (1979).
Avendano et al.,“The Problem of the Existence of C(Ar)-H. N Intramolecular Hydrogen Bonds in a Family of 9-azaphenyl-9H-carbazoles”,J. Chem. Soc. Perkin Trans. 2, pp. 1547-1555, (1993).
Duplantier et al.;“7-Oxo-4,5,6,7-tetrahydro-1H-pyrazolo[3,4-c] pyridines as Novel Inhibitors of Human Eosinophil Phosphodiesterase”, J. Med. Chem. 41: 2268-2277, (1998).
Goodbrand and Hu;“Ligand-Accelerated Catalysis of the Ullmann Condensation: application to Hole Conducting Triarylamines”,J. Org. Chem. 64: 670-674, (1999).
Greiner Alfred;“An Improvement of the N-Arylation of Amides; Application to the Synthesis of Substituted 3-(N-Acetyl-N-phenylamino)-pyridines”,Synthesis No. 4: 312-313, (Apr. 1989).
Gauthier and Frechet;“Phase-Transfer Catalysis in the Ullmann Synthesis of Substituted Triphenylamines”,Synthesis, No. 4: 383-385, (Apr. 1987).
Gujadhur et al.; “Formation of Aryl-nitrogen Bonds Using Soluble Copper (1) Catalyst”, tetrahedron letters 42: 4791-4793, (2001).
Ito et al.;“Synthesis of Oligo (m-aniline)”, Tetrahedron Letters 36(48): 8809-8812, (1995).
Joyeau et al.;“Synthesis of Benzocarbacephem and Benzocarbacephem Derivatives by Copper-Promoted Intramolecular Aromatic Substitution”,J. Chem. Soc. Perkin Trans. 1 , pp. 1899-1907, (1987).
Kametani et al.;“Studies on the Synthesis of Heterocyclic Compounds. Part 865.1/7A Novel Synthesis of Indole Dervatives by Intramolecular Nucleophilic Aromatic Substitution”,J.C. S. Perkin I, pp. 290-294, (1981).
Kang et al.;“Copper-Catalyzed N-Arylation of Amines with Hypervalent Iodonium Salts”,Synlett No. 7: 1022-1024, (2000).
Kato et al.;“Water-Soluble Receptors For Cyclic-AMP and Their Use for Evaluation Phosphate-Guanidinium Interactions”,J. Am. Chem. Soc. 116: 3279-3284, (1994).
Lexy and Kaufmann;“Synthese, Lithiierung und Oxidative Kupplung von 1,3,5-Tri(1-Pyrazoly) benzol”, Chem. Ber. 113: 2755-2859 (1980).
Lindley James;“Copper Assisted Nucleophilic Substitution of Aryl Halogen”, Tetrahedron 40(9): 1433-1456, (1984).
Murakami et al.; Fisher Indolization of Ethyl Pyruvate 2-[2-(Trifluoromethyl) Phenyl]- Phenylhydrazone and New Insight Into the Mechanism of the Goldberg Reaction. (Fisher Indolization and Its Related Compounds. XXVI1), Chem. Pharm. Bull. 43(8); 1281-1286 (1995).
Palkowitz et al.;“Discovery and Synthesis of [6-Hydroxy-3-[4-[2-(1-piperidinyl)ethoxy] phenoxy]-2-(4-Hydroxyphenyl)] benzo[b] thiophene: A Novel, Highly Potent, Selective Estrogen Receptor Mdoulator”,Journal od Medicinal Chemistry 40(10): 1407-1416, (May 9, 1997).
Renger Bernd;“Direkte N-Arylierung von Amiden: Eine Verbesserung der Goldberg-Reaktion”,Synthesis, No. 9: 856-860, (1985).
Sugahara and Ukita,“A Facile Copper-Catalyzed Ullmann Condensation: N-Arylation of Heterocyclic Compounds Containing an-NHCO-Moiety”, Chem. Pharm. Bull. 45(4): 719-721 (1977).
Sawyer et al.;“Synthesis of Diaryl Ethers, Diaryl Thioethers, and Diarylamines Mediated by Potassium Fluoride- Alumina and 18-Crown-6: Expansion of Scope and Utility”,J. Org. Chem. 63: 6338-6343, (1998).
Smith III and Sawyer,“A Novel and Selective Method for the N-Arylation of Indoles Mediated by KF/ Al2O3”, Tetrhedron Letters 37(3): 299-302, (1996).
Smith III and Sawyer,“An SNAr-Based Preparation of 1-(2,3-, and 4-Pyridyl) Indoles Using Potassium Fluoride/ Alumina”,Heterocycles51(1): 157-160, (1999).
Tokmakov and Grandberg;“Rearrangement of 1-Arylindoles to 5H-Dibenz[b, f]azepines”,Tetrahedron 51(7): 2091-2098, (1995).
Unangst et al.;“Synthesis of Novel 1-Phenyl-1H-Indole-2-Carboxylic Acids. I Utilization Of Ulmann and Dieckmann Reactions for the Prepartion of 3-Hydroxy, 3-Alkoxy, and 3-Alkyl Derivatives”,Journal of Heterocyclic Chemistry, 24(3): 811-815, (May-Jun. 1987).
Vedejs E.;“Substituted Isoquinolines by Noyori Transfer Hydrogenation: Enantioselective Synthesis of Chiral Diamines Containing an aniline Subunit”, J. Org. Chem. 64: 6724-6729, (1999).
Yamamoto and Kurata;“Ullmann Condensation Using Copper or Copper Oxide as the Reactant. Arylation of Active Hydrogen Compounds (imides, amides, amines, phenol, benzoic acid, and phenylacetylene)”, Can. J. Chem. 61: 86-91, (1983).
Fabian, “Kinetics and Mechanism of Complex-formation Reactions of Ammonia and Methylamine With
Antilla Jon C.
Buchwald Stephen L.
Hennessy Edward J.
Job Gabriel E.
Klapars Artis
Foley & Hoag LLP
Gordon Dana M.
Massachusetts Institute of Technology
Raymond Richard L.
Tucker Zachary C.
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