Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2006-03-15
2010-02-16
Saeed, Kamal A (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C548S954000, C548S962000
Reexamination Certificate
active
07662969
ABSTRACT:
This invention relates to compositions and methods for achieving the efficient aziridination of organic molecules, especially olefins. More specifically, the invention is directed to a mild, selective, and efficient aziridination protocol that involves catalysis by a mixed-valent dirhodium(II,III) catalyst (Rh25+). Especially preferred sources for forming such mixed-valent dirhodium(II,III) catalyst (Rh25+) are dirhodium(II) carboxamidates, such as dirhodium(II) caprolactamate, and their derivatives and analogues.
REFERENCES:
patent: 4026709 (1977-05-01), Piller et al.
patent: 4840890 (1989-06-01), Kamei et al.
patent: 5703246 (1997-12-01), Aggarwal et al.
patent: 5712331 (1998-01-01), Ryang
patent: 5929252 (1999-07-01), Sharpless et al.
patent: 5936127 (1999-08-01), Zhang
patent: 6258960 (2001-07-01), Antilla et al.
patent: 6307087 (2001-10-01), Buchwald et al.
patent: 6395916 (2002-05-01), Buchwald et al.
patent: 6946560 (2005-09-01), Buchwald et al.
Guthikonda, Kiran. A Unique and Highly Efficient Method for Catalytic Olefin Aziridination. Journal of the American Chemical Society. 124 (2002) 13672-13673.
Ali, S. I. et al., “Pyridinium Hydrobromide Perbromide: A Versatile Catalyst for Aziridination of Olefins Using Chloramine-T,”Org. Lett.1999 1(5); 705-707.
Anada, M. et al., “A New Dirhodium(Ii) Carboxamidate Complex As A Chiral Lewis Acid Catalyst for Enantioselective Hetero-Diels-Alder Reactions,”Angew. Chem., Int. Ed., 2004 43:2665.
Angeles-Boza, A.M. et al., “DNA Binding and Photocleavage in Vitro by New Dirhodium(II) dppz Complexes: Correlation to Cytotoxicity and Photocytotoxicity,”Inorg. Chem.2004 43:8510-8519.
Berry, J.F. et al., “A Hardwon Dirhodium Paddlewheel With Guanidinate Type (Hpp) Bridging Ligands,”Dalton Trans.2005 7; (23):3713-3715.
Bode, J.W . et al., “Intramolecular Regioselective Insertion into Unactivated Prochiral Carbon-Hydrogen Bonds with Diazoacetates Catalyzed by Chiral Dirhodium(II) Carboxamidates. Highly Enantioselective Total Synthesis of Natural Lignan Lactones,”J. Org. Chem.1996 61:9146-9155.
Catino, A.J. et al., “Dirhodium(II) Caprolactamate: An Exceptional Catalyst for Allylic Oxidation,”J. Am. Chem. Soc.2004 126(42):13622-13623.
Catino, A.J. et al., “Efficient Aziridination Of Olefins Catalyzed By Mixed-Valent Dirhodium(II,III) Caprolactamate,”Org. Lett.2005 7(13):2787-2790.
Chifotides, H.T. et al., “Interactions of Metal-Metal-Bonded Antitumor Active Complexes with DNA Fragments and DNA,”Acc. Chem. Res.2005 38:146-156.
Cotton, F.A. et al., “The First Dirhodium Tetracarboxylate Molecule Without Axial Ligation: New Insight Into The Electronic Structures Of Molecules With Importance In Catalysis And Other Reactions,”J. Am. Chem. Soc.2002 124(20):5658-5660.
Cui, Y. et al., “Efficient Aziridination Of Olefins Catalyzed By A Unique Disilver(I) Compound,”J. Am. Chem. Soc.2003 125(52):16202-16203.
Dauban, P. et al., “Synthesis of Cyclic Sulfonamides via Intramolecular Copper-Catalyzed Reaction of Unsaturated Iminoiodinanes,”Org. Lett.2000 2(15):2327-2329.
Dauban, P. et al., “Copper-Catalyzed Nitrogen Transfer Mediated By Iodosylbenzene PHI=O,”J. Am. Chem. Soc.2001 123:7707-7708.
Dauban, P. et al., “Intramolecular Bromine-Catalyzed Aziridination: A New Direct Access To Cyclic Sulfonamides,”Tetrahedron Lett.2001 42:1037-1040.
Dauban, P. et al., “Iminoiodanes and C-N Bond Formation in Organic Synthesis,”Synlett2003:1571.
Dequeant ,M.Q. et al., “Dirhenium Paddlewheel Compounds Supported by N,N′-Dialkylbenzamidinates: Synthesis, Structures, and Photophysical Properties,”Inorg. Chem.2004 43:7887-7892.
Doyle, M. P. et al., “The Influence of Ligands on Dirhodium(II) on Reactivity and Selectivity in Metal Carbene Reactions,”Prog. Inorg. Chem.2001 49:113-168.
Doyle, M.P., “Asymmetric syntheses with catalytic enantioselective metal carbene transformations,”Russ. Chem. Bull.1994 43: 1770-1782.
Doyle, M.P., “Enantiomer Differentiation in Intramolecular Carbon-Hydrogen Insertion Reactions of Racemic Secondary Alkyl Diazoacetates Catalyzed by Chiral Dirhodium(II) Carboxamidates,”Russ. Chem. Bull.1995 44:1729-1734.
Doyle, M.P. et al., “Dirhodium(II) Tetrakis(Carboxamidates) with Chiral Ligands. Structure and Selectivity in Catalytic Metal Carbene Transformations,”J Am. Chem. Soc.1993 115:9968-9978.
Doyle, M.P. et al., “Electronic And Steric Control In Carbon-Hydrogen Insertion Reactions Of Diazoacetoacetates Catalyzed By Dirhodium(II) Carboxylates And Carboxamides,”J. Am. Chem. Soc.1993 115(3):958-964.
Doyle, M.P. et al., “Enhancement of Enantiocontrol/Diastereocontrol in Catalytic Intramolecular Cyclopropanation and Carbon-Hydrogen Insertion Reactions of Diazoacetates with Rh2(4S-MPPIM)4”Tetrahedron Lett.1995 36:7579-7582.
Doyle, M.P. et al., “Highly Enantioselective Route to β-Lactams via Intramolecular C-H Insertion Reactions of Diazoacetylazacycloalkanes Catalyzed by Chiral Dirhodium(II) Carboxamidates,”Synlett1995 1075-1076.
Doyle, M.P. et al., “Optimization of Enantiocontrol for Carbon-Hydrogen Insertion with Chiral Dirhodium(II) Carboxarnidates. Synthesis of Natural Dibenzylbutyrolactone Lignans from 3-Aryl-1-propyl Diazoacetates in High Optical Purity,”J. Org. Chem.1995 60:6654-6655.
Doyle, M.P. et al., “Chiral Dirhodium Carboxamidates. Catalysts for Highly Enantioselective Syntheses of Lactones and Lactams,”Aldrichimica Acta1996 29(1):3-11.
Doyle, M.P. et al., “Highly Enantioselective Intramolecular Cyclopropanation Reactions of N-Allylic-N-methyldiazoacetamides Catalyzed by Chiral Dirhodium(II) Carboxamidates,”J. Org. Chem.1996 61:2179-2184.
Doyle, M.P. et al., “Highly Enantioselective Oxonium Ylide Formation and Stevens Rearrangement Catalyzed by Chiral Dirhodium(II) Carboxamidates,”Tetrahedron Lett.1997 38:4367-4370.
Doyle, M.P. et al., “Enantiocontrol in the Generation and Diastereoselective Reactions of Oxonium Ylides Catalyzed by Chiral Dirhodium(II) Carboxamidates. Metal-Stabilized Ylides as Reaction Intermediates,”J. Am. Chem. Soc.1998 120:7653-7654.
Doyle, M.P. et al., “Recent Advances in Asymmetric Catalytic Metal Carbene Transformations,”Chem. Rev.1998 98:911-935.
Doyle, M.P. et al., “Dirhodium(II) Tetrakis[methyl 2-oxaazetidine-4-carboxylate]: A Chiral Dirhodium(II) Carboxamidate of Exceptional Reactivity and Selectivity,”Organic Lett.2000 2:1145-1147.
Doyle, M.P. et al., “Optimization of Enantiocontrol in cis-Selective Cyclopropanation Reactions Catalyzed by Dirhodium(II) Tetrakis-[alkyl 2-oxaazetidine-4(S)-carboxylates],”J. Chem. Soc. Chem. Commun.2000 867-868.
Doyle, M.P. et al., “A New Class of Chiral Lewis Acid Catalysts for Highly Enantioselective Hetero-Diels-Alder Reactions: Exceptionally High Turnover Numbers from Dirhodiurn(II) Carboxamidates,”J. Am. Chem. Soc.2001 123:5366-5367.
Doyle, M.P. et al., “Epoxides and aziridines from diazoacetates via ylide intermediates,”Org. Lett.2001 3(6):933-935.
Doyle, M.P. et al., “High Selectivity from Configurational Match/Mismatch in Carbon-Hydrogen Insertion Reactions of Steroidal Diazoacetates Catalyzed by Chiral Dirhodium(II) Carboxamidates,”J. Org. Chem.2001 66:8112-8119.
Doyle, M.P. et al., “Reactivity Enhancement for Chiral Dirhodium(II) Tetrakis (Carboxamidates),”Adv. Synth. Cat.2001 343(1):112-117.
Doyle, M.P. et al., “Enantioselective Carbon-Hydrogen Insertion is an Effective and Efficient Methodology for the Synthesis of (R)-(−)-Baclofen,”Chirality2002 14:169-172.
Doyle, M.P. et al., “Highly Selective Synthesis of a 2-Deoxyxylolcatam via Enantioselective Carbon-Hydrogen Insertion Reactions Using Chiral Dirhodium(II) Carboxamidates,”Adv. Synth. Cat.2002 344:91-95.
Doyle
Auerbach Jeffrey I.
Edell Shapiro & Finnan LLC
Saeed Kamal A
Shterengarts Samantha L
University of Maryland College Park
LandOfFree
Efficient aziridination of olefins catalyzed by dirhodium... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Efficient aziridination of olefins catalyzed by dirhodium..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Efficient aziridination of olefins catalyzed by dirhodium... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-4164715