Catalytic compositions and methods for asymmetric allylic...

Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...

Reexamination Certificate

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C544S224000, C544S226000, C556S063000, C556S057000, C556S061000, C556S062000

Reexamination Certificate

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07005521

ABSTRACT:
Complexes of a selected class of chiral ligands with molybdenum, tungsten or chromium, preferably molybdenum, are effective as catalysts in highly enantioselective and regioselective alkylation of allylic substrates. Such compositions provide a versatile and low-cost alternative to existing catalysts.

REFERENCES:
Dvorák, D., et al., “Stereochemistry of Molybdenum (O) -Catalyzed Allylic Substitution: The First Observation of a Syn-Syn Mechanism,”J. Am. Chem. Soc. 117:6130-6131 (1995).
Faller, J.W., and Linebarrier, D., “Reversal of Stereochemical Path in Allylic Alkylations Promoted by Palladium and Molybdenum Complexes,”Organometallics 7:1670-1672 (1988).
International Search Report for Application No. PCT/GB98/03850.
Lloyd-Jones, G.C., and Pfaltz, A., “Chiral Phosphanodihydrooxazoles in Asymmetric Catalysis: Tungsten-Catalyzed Allylic Substitution,”Angew. Chem. Int. Ed. Engl. 34(4):462-464 (1995).
Rubio, A., and Liebeskind, L.S., “Enantiospecific Synthesis by Transformations of Chiral Pool-Derived Metalπ-Complexes. A Strategy for the Introduction of Substituents on a Pyranose-Derived Lateralπ-Ligand either Syn or Anti to the Coordinating Metal,”J. Am. Chem. Soc. 115:891-901 (1993).
Trost, B.M., and Lautens, M., “Chemoselectivity and Stereocontrol in Molybdenum-Catalyzed Allylic Alkylations,”J. Am. Chem. Soc. 109:1469-1478 (1987).
Trost, B.M., and Lautens, M., “Regiochemical Diversity in Allylic Alkylations via Molybdenum Catalysts,”Tetrahedron 43:21 (4817-4840 (1987).
Trost, B.M., and Merlic, C.A., “Ligand Dependence of Molybdenum-Catalyzed Alkylations. Molybdenum-Isonitrile Complexes as a New Class of Highly Reactive Alkylation Catalysts,”J. Am. Chem. Soc. 112:9590-9600 (1990).
Trost, B.M., and Van Vranken, D.L., “Asymmetric Ligands for Transition-Metal-Catalyzed Reactions: 2-Diphenylphosphinobenzoyl Derivatives of C2-Symmetric Diols and Diamines,”Angew. Chem. Int. Ed. Engl. 31(2):228-230 (1992).
Trost, B.M., et al., “A Modular Approach for Ligand Design for Asymmetric Allylic Alkylations via Enantioselective Palladium-Catalyzed Ionizations,”J. Am. Chem. Soc. 114:9327-9343 (1992).

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