Chiral metallocene compounds and preparation thereof by creation

Chemistry of hydrocarbon compounds – Alicyclic compound synthesis

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585375, 556 43, 556 47, 556 53, 556 60, 556143, C07C 1300, C07C 202

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053491009

ABSTRACT:
There are provided enantiomerically enhanced chiral substituted cyclopentadienyl ligands, and compounds thereof, and a process for their making comprising contacting an optionally substituted fulvene having a prochiral carbon 6 with a lithium salt of an amine, amino acid or amide to effectuate enantioselective hydride addition to the carbon 6 of the fulvene so as to create a chiral center. There are further provided enantiomerically enhanced chiral organometallic complexes having one or more chiral substituted cyclopentadienyl groups.

REFERENCES:
Morrison et al., Organic Chemistry, 3rd Ed., Allyn and Bacon Inc., Boston, pp. 123-125 (1973).
Daniel T. Mallin et al., "Synthetic, X-ray structural and polymerization studies on isopropyltetramethylcyclopentadienyl derivatives of titanium", J. Organomet Chem., vol. 381, 1990, pp. 35-44.
Jerome C. Pando, Eric Mintz, "5-Methoxy-2,3,4,5-tetramethylcyclopent-2-enone, a Synthetic Equivalent For 2,3,4,5-Tetramethylcyclopentadienone: Application to the Synthesis of 1,2,3,4-Tetramethylfulvene", Tetrahedron Letters, vol. 30, No. 36, 1989, pp. 4811-1812.
Gerhard Erker et al., "Double Stereodifferentiation in the Formation of Isotactic Polypropylene at Chiral (C.sub.5 H.sub.4 CHMePh).sub.2 ZrCl.sub.2 /Methylalumoxane Catalysts", Angew. Chem. Int. Engl. 28, 1989 No. 5, pp. 628-629.
Dennis M. Bensley, Jr. and Eric A. Mintz, "1,2,3,4,6-Pentamethylfulvene: a convenient precursor to substituted tetramethylcyclopentadienyl transition metal complexes" J. Organomet. Chem., vol. 353, 1988, pp. 93-103.
Dennis M. Bensely, Jr. et al. "Synthesis of [C.sub.5 (CH.sub.3).sub.4 H]CH.sub.2 CH.sub.2 CH.sub.2 P(C.sub.6 H.sub.5).sub.2 : A Novel Heterodifunctional Ligand Possessing Both a Tetramethylcyclopentadiene and a Remote Diphenylphosphine Functionality". J. Org. Chem., vol. 53, 1988, p. 4417.
Ronald L. Halterman and K. Peter C. Hollhardt, "Synthesis and Asymmetric Reactivity of Enantiomerically Pure Cyclopentadienyl metal Complexes Derived from the Chiral Pool", Organometallics, 1988, vol. 7, pp. 883-892.
Emilio E. Bunel et al., "Synthesis of p-Phenylene- and p-Biphenylene-Bridged Methylated Bionuclear Ferrocenes" Organometallics, vol. 7 No. 2, 1988, pp. 474-476.
George W. Parshall, William A. Nugent, "Making pharmaceuticals via homogeneous catalysis", Chemtech, Mar. 1988, pp. 184-190.
George W. Parshall and William A. Nugent, "Functional chemicals via homogeneous catalysts", Chemtech, May 1988, pp. 314-320.
George W. Parshall, William A. Nugent, "Homogeneous catalysis for agrochemicals, flavors, and fragrances", Chemtech, Jun. 1988, pp. 376-383.
Paavoo O.sub.5. Lumme and Urho Turpeinen, "Crystal and molecular structure of [3-(.sup.5 n-tetramethylcyclopentadienyl)-1-(n.sup.6 -meisityl)propane]ieridium(II) bistetrafluoroborate mononitromethane", J. Organomet. Chem., vol. 348, 1988, pp. 255-260.
Gallucci, et al. "Bis(isodicyclopentadienyl) Complexes of the Goup 4 Transition Metals. Stereoselective Synthesis and Crystal Structures of the Titanocene and Zirconocene Dichloride Derivatives" Organometallics, vol. 6, 1987, pp. 15-19.
J. F. Buzinkai and R. R. Schrock, "Heterobimetallic Complexes Connected by Peralkylated Cyclopentadienyl Rings" Organometallics, vol. 6, 1987, pp. 1447-1452.
Ronald L. Halterman et al., "A designed, Enantiomerically Pure, Fused Cyclopentadienyl Ligand with C.sub.2 Symmetry: Synthesis and Use in Enantioselective Titanocene-Catalyzed Hydrogenations of Alkenes", J. Am. Chem. Soc., vol. 109, 1987, pp. 8105-8107.
N. E. Schore and B. E. LaBelle, "Reactions of [(Diphenylphosphino)methyl]lithium with Dimethylfulvene", J. Org. Chem., vol. 46, 1987, pp. 2306-2310.
H. M. R. Heffmann and Oskar Koch, "Regioselective Preparation of Vinylcyclopentadienes and Selected Cycloaditions", J. Oreg. Chem, vol. 51, 1986, pp. 2939-2944.
Leo A., Paquette, et al., ".pi.-Facial Stereoselectivity Operational during Conversion of Isodicyclopentadienes to Metallocene Derivatives", Organometallics, vol. 5, 1986, pp. 490-499.
Lihong Shen and Eric A. Minz, "Novel Reduction of 6-t Butylfulvene by Diethylaminolithium and 1,2,3,4-Tetrahydroisoquinolinyllithium" submitted to Tetrahedron Letters, Jan. 1981.
Jerome C. Pando, et al., "5-Methyoxy-and 5-Phenoxy-2,3,4,5-Tetramethylcyclopent-2-Enone as Synthetic Equivalents for 2,3,4,5-Tetramethylcyclopentadienone; Synthesis of 1,2,3,4-Tetramethylfulvene and 1,2,3,4,6-Pentamethylfulvene", Tetrahedron Letters, vol. 30, 1989.
H. B. Kagan, "Chiral Ligands in Asymmetric Catalysis By Transition Metal Complexes", Annals New York Academy of Sciences, 1980, pp. 1-15.
Jack Hine and David B. Knight, "Base-Catalyzed Deuterium Exchange of 6,6-Dimethylfulvene" J. Org. Chem, vol. 45, 1980, pp. 991-998.
William F. Little and Robert C. Koestler, "Preparation of Substituted Ferrocenes from Fulvenoid Compounds", J. Org. Chem., vol. 26, Sep. 1961, pp. 3245-3247.
David B. Knight, et al., "Protonation and Deuteration of the Isopropenylcyclopentadienyl Anion. Trapping of the Isomeric Product Mixture", J. Org. Chem., vol. 37, No. 5, 1972, pp. 688-692.
Jack Hine and David B. Knight, "Protonation of the Isopropenylcyclopentadienyl Anion", J. Org. Chem., vol. 35, No. 11, 1970, pp. 3946-3949.
Carol M. Fendrick, et al. Organometallics, vol. 3, 1983, pp. 819-812.
S. Couturier and B. Gautheron, "Synthesis and Reactions of Substituted Zirconocene and Hafnocene Dimethyls and the Corresponding Dihydrides", J. Organomet. Chem., vol. 157, 1978, pp. C61-C63.
P. Renault, et al., "Chlorures De Mono-et Dialkyl-Zirconocene et-Hafnocene", J. Organomet. Chem., vol. 148, 1978, pp. 35-42.
J. C. LeBlanc and C. Moise, "Complexes Derives Du Dichlorure De Titanocene A Pseudoasymetrie Centrometallee", J. Organomet. Chem., vol. 131, 1977, pp. 35-42.
S. Couturier et al., "Synthese Et Reactivite de Nouveaux Dihydrurozirconocenes et Hafnocenes substitues Achiraux et Chiraux", J. Organomet. Chem., vol. 195, 1980, pp. 291-306.
Franz Wochner, et al., "Syntheses and Crystal Structures of Ethylene-Bridged Titanocene and Zirconocene Derivatives with Permethylated Ring Ligands", J. Organomet. Chem., vol. 288, 1985, pp. 69-77.
Richard S. Threlkel and John E. Bercaw, "A convenient Synthesis of alkyltetramethylcyclopentadienes and Phenyltetramethylcyclopentadiene", J. Organomet. Chem., vol. 136, 1977, pp. 1-5.
H. J. Scholz and H. Werner, "Synthese Von Li.sub.2 [C.sub.5 Me.sub.4).sub.2 CH.sub.2 ]Und Ringverbruckter Rhodiium-Zeikernkomplexe Mit Dem (C.sub.5 Me.sub.4).sub.2 CH.sub.2 -Dianion Als Burckenliganden", J. Org. Chem., vol. 303, 1986, pp. C-8-C12.
David Feitler and George M. Whitesides, "Convenient Preparations of 1,2,3,4,5-Pentamethylcyclopentadiene and 1-Ethyl-2,3,4,5-tetramethylcyclopentadiene", Inorg. Chem., vol. 15, No. 2, 1976, pp. 466-469.
Donald J. Cram and Donalr R. Wilson, "Studies in Stereochemistry. XXXIII. Approaches to Models for 1,3-ASymmetric Induction", J. Am. Chem. Soc., vol. 85, May 5, 1963, pp. 1249-1257.
Gilbert M. Brown and Norman Sutin, "A Comparison of the Rates of Electron Exchange Reactions of Ammine Complexes of Ruthenium (II) and-(III) with the Predictions of Adiabatic, Outer-Sphere Electron Transfer Models", JACS, vol. 101, No. 4, pp. 883-895 (1979).
William S. Knowled, "Asymmetric Hydrogenation", Acc. Chem. Res., vol. 15, 1983, pp. 106-112.
Charles P. Casey, et al., "Synthesis of Molybdenum-Rhodium and Molybdenum-Iridium Compounds Linked by a Heterodifunctional Ligand and Formation of Molybdenum-Iridium Dihydrides by Reaction with Molecular Hydrogen", J. Am. Chem. Soc., vol. 105, 1983, pp. 7574-7580.
M. F. Semmelhack et al., "Reduction of Coordinated Carbon Monoxide to `Zirconoxy` Carbenes with Permethylzirconocene Dihydride", J. Am. Chem. Soc., vol. 101:1, Jan. 3, 1979, pp. 218-220.
Josephine Paw Blaha and Mark S. Wrighton, "Relative Importance of Dissociative Loss of Carbon Monoxide and Formation of Benzyl Radicals from Photoexcitation of (n.sup.5 -C.sub.5 R.sub.5)Fe(CO).sub.2 (.sup.1 n-CH.sub.2 C.sub.6 H.sub.5) and Evidence for Reaction of Carbon Monoxide with 17-Electron Radicals", J. Am. Chem. Soc., vol. 107, 1985, pp. 2694-2702.
Donald J. Harvan, et a

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