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United States Patent (19) 11 Patent Number: 5,936,127 Zhang (45) Date of Patent: Aug USOO5936127A United States Patent (19) 11 Patent Number: 5,936,127 Zhang (45) Date of Patent: Aug. 10, 1999 54 ASYMMETRIC SYNTHESIS AND CATALYSIS Jacobsen, E.N., “Asymmetric Catalytic Epoxidation of WITH CHIRAL, HETEROCYCLIC Unfunctionalized Olefins,” Catalytic Asymmetric Synthesis, COMPOUNDS Chapter 4.2, 159-202 (1993). Smith, M.B., “Retrosynthesis, Stereochemistry and Confor 75 Inventor: Xumu Zhang, State College, Pa. mations,” Organic Synthesis, Chapter 1.4.C., 58-63 (1994). Trost, B.M. & Li, C.-J., “Novel Umpolung in C-C Bond 73 Assignee: The Penn State Research Foundation, Formation Catalyzed by Triphenylphosphine,” J. AM. University Park, Pa. Chem. Soc., 116, 31.67-3168 (1994). Zhang, C. & Lu, X., “Phosphine-Catalyzed Cycloaddition 21 Appl. No.: 09/006,178 of 2,3-Butadienoates or 2-Butynoates with Electron-Defi cient Olefins. A Novel 3+2 Annulation Approach to Cyclo 22 Filed: Jan. 13, 1998 pentenes,” J. Org. Chem. 60,2906–2908 (1995). Aggarwal, V.K. et al., “A Novel Catalytic Cycle for the Related U.S. Application Data Synthesis of Epoxides Using Sulfure Ylides,” Chem. Eur: 60 Provisional application No. 60/035,187, Jan. 13, 1997, and Journal, 1024–1030 (1996). provisional application No. 60/046,117, May 9, 1997. Aggarwal, V.K., et al., “Direct Asymmetric Epoxidation of Aldehydes Using Catalytic Amounts of Enantiomerically 51 Int. Cl. ........................... C07F 9/02; CO7D 333/50; Pure Sulfides,” J. Am. Chem. Soc., 118, 7004-7005 (1996). 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Ber, 119, Garrett & Dunner, LLP 3326–3343 (1986). 57 ABSTRACT Drewes, S.E. & Roos, G., “Synthetic Potential of the Tetia ry-Amine-Catalysed Reaction of Activated Vinyl Carban This invention relates to chiral heterocyclic compounds ions with Aldehydes.” Tetrahedron, 44, 4653-4670 (1988). useful for asymmetric Synthesis and catalysis. More Noyori, R. & Kitamura, M., “Enantioselective Catalysis particularly, the invention relates to chiral heterocyclic with Metal Complexes. An Overview,” Modern Synthetic phosphine, Sulfur, and nitrogen compounds for asymmetric Methods, 116–198 (1989). Synthesis and catalysis in the production of enantiomerically Trost, B.M. & Fleming, I., “Transition Metal Mediated pure products. Cycloadditions,” Comprehensive Organic Synthesis, Chap ter 3.2, 271-314 (1991). 20 Claims, No Drawings 5,936,127 Page 2 OTHER PUBLICATIONS Kozikowski, A. P. & Jung, S. 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M., “3+2 Cycloaddition Approaches to Five Achiwa, K., “Asymmetric Hydrogenation with New Chiral Membered Rings via Trimethylenemethane and Its Equiva Functionalized Bisphosphine-Rhodium Complexes,” J. Am. lents.” Angew. Chem. Int. Ed. Engl., 25, 1-20 (1986). Chem. Soc., 98, 8265-8266 (1976). Binger, P. & Bich, H.M., “Cyclopropenes and Methylenecy Corey, E.J., et al., “New Reagents for the Intermolecular and lopropanes as Multifunctional Reagents in Transition Metal Intramolecular Pinacolic Coupling of Ketones and Alde Catalyzed Reactions,” Topics in Current Chemistry, 135, hydes,” J. Org. Chem., 41, 260–265 (1977). 77-151 (1987). Fry Zuk, M.D. & Bosnich, B., “Asymmetric Synthesis. Pro Halterman, R.L., et al., “ADesigned, Enantiomerically Pure, duction of Optically Active Amino Acids by Catalytic Fused Cyclopentadienyl Ligand with C. Symmetry: Syn Hydrogenation.” J. Am. Chem. Soc., 99, 6262–6267 (1977). thesis and Use in Enantioselective Titanocene Catalyzed Vineyard, B.D., et al., “Asymmetric Hydrogenation. Hydrogenation of Alkenes,” J. Am. Chem. Soc. 109, Rhodium Chiral Bisphosphine Catalyst,” J. Am. Chem. 8105–8106 (1987). Society, 99,5946–5952 (1977). Schlessinger, R.H. & Iwanowicz, E.J., “The Synthesis of Whitesell, J.K. & Felman, S.W., “Asymmetric Induction. 2. Either (+) or (-) Trans-2,5-Dimethylpyrrolidine,” Tetrahe Enantioselective Alkylation of Cyclohexanone via a Chiral dron Lett., 28, 2083–2086 (1987). Enamine,” J. Org. Chem, 42, 1663 (1977). Tomioka, K., et al., “Enantioface Differentiation in Cis Kauffmann, T., “In Search of New Organometallic Reagents Dihydroxylation of C-C Double Bonds by Osmium for Organic Synthesis,” Topics in Curr: Chem., 92, 111-147 Tetroxide with Use of a Chiral Diamine with D symmetry,” (1980). J. Am. Chem. Soc., 109, 6213–6215 (1987). A. Miyashita, et al., “2,2'-Bis(Diphenylphosphino)-1,1'-Bi Brunner, H., “Enantioselective Synthesis with Optically naphthyl (BINAP), an Atropisomeric Chiral Bis(traryl)phos Active Transition-Metal Catalysts,” Synthesis, 645-654 phino, and Its Use in the Rhodium(I)-Catalyzed Asymmet (1988). ric Hydrogenation of C-(Acylamino)acrylic Acids,” J. Am. Feldman, K. S., et al., “Cyclopentane Synthesis via Free Chem. Soc., 102,7932–7934 (1980). Radical-Mediated Addition of Funtionalized Alkenes to Ojima, I. & Yoda, N., “N-Carbamoyl-4- Diphenylphos Substituted Vinylcyclopropanes,” J. Am. Chem. Soc., 110, phino-2- Diphenylphosphinomethylphyrrolidines (CAPP). 3300–3302 (1988). Efficient New Chiral Ligands for Asymmetric Hydrogena Goodridge, R.J., et al. “Preparation of Stable, Camphor tion.” Tetrahedron Lett., 21, 1051–1054 (1980). Derived, Optically Active Allyl and Alkyl Sulfoxides and Danheiser, R.L., et al. "(Trimethylsilyl)cyclopentene Annu Thermal Epimerization of the Allyl Sulfoxides,” J. 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