The transition metal-catalyzed selective oxidation of unreactive carbon-hydrogen bonds is a direct method or forming alcohols and carbonyl compounds from hydrocarbons under mild conditions. Inspired by remarkable catalytic activity of metalloenzymes in nature, extensive research has been focused on the development of practical catalytic methods for C-H bond oxidation reactions that utilize molecular oxygen as the sole oxidizing agent under environmentally benign conditions. This group has been exploring the activity of highly unsaturated ruthenium complexes with oxygen and nitrogen donor ligands for C-H bond activation reactions. The proposed research presents the detailed plans for studying C-H bond oxidation reactions mediated by novel bimetallic ruthenium-hydroxo complexes.Ihe second part of the proposed research focuses on the catalytic addition reactions of alkenes. In particular, metal-catalyzed conjugate addition of nitrogen and oxygen nucleophiles has been shown to be an effective method for forming a wide variety of biologically important beta-amino acids and -alkoxy ketones. Another reaction of current interest is the asymmetric hydrovinylation of alkenes, which has been shown to be a versatile method for forming new C-C bonds. The proposed research focuses on the development of highly effective chiral ruthenium catalysts for asymmetric conjugate addition of alcohols and hydrovinylation of alkenes. The detailed plans for examining the mechanisms of these reactions are also presented.The proposed research employs well-defined ruthenium-hydroxo and -amido complexes to effect catalytic C-H bond oxidation, conjugate addition of alcohols and hydrovinylation of alkenes. The proposed research seeks for both fundamental mechanistic understandings and the development of effective ruthenium catalysts for asymmetric conjugate addition of alcohols and hydrovinylation of alkenes.

National Institute of Health (NIH)
National Institute of General Medical Sciences (NIGMS)
Academic Research Enhancement Awards (AREA) (R15)
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Medicinal Chemistry Study Section (MCHA)
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Schwab, John M
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Marquette University
Schools of Arts and Sciences
United States
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Kwon, Ki-Hyeok; Lee, Do W; Yi, Chae S (2012) Scope and Mechanistic Study of the Coupling Reaction of ?, ?-Unsaturated Carbonyl Compounds with Alkenes: Uncovering Electronic Effects on Alkene Insertion vs Oxidative Coupling Pathways. Organometallics 31:495-504
Kwon, Ki-Hyeok; Lee, Do W; Yi, Chae S (2011) Tetrasubstituted olefins through the stereoselective catalytic intermolecular conjugate addition of simple alkenes to ?,?-unsaturated carbonyl compounds. Angew Chem Int Ed Engl 50:1692-5
Yi, Chae S (2011) Recent advances in the synthetic and mechanistic aspects of the ruthenium-catalyzed carbon-heteroatom bond forming reactions of alkenes and alkynes. J Organomet Chem 696:76-80
Yi, Chae S; Lee, Do W (2010) Intermolecular Dehydrative Coupling Reaction of Arylketones with Cyclic Alkenes Catalyzed by a Well-Defined Cationic Ruthenium-Hydride Complex: A Novel Ketone Olefination Method via Vinyl C-H Bond Activation. Organometallics 29:1883-1885
Gao, Ruili; Yi, Chae S (2010) Regioselective formation of alpha-vinylpyrroles from the ruthenium-catalyzed coupling reaction of pyrroles and terminal alkynes involving C-H bond activation. J Org Chem 75:3144-6
Lee, Do W; Yi, Chae S (2010) Chain- and Regioselective Ethylene and Styrene Dimerization Reactions Catalyzed by a Well-Defined Cationic Ruthenium-Hydride Complex: New Insights on the Styrene Dimerization Mechanism. Organometallics 29:3413-3417
Kwon, Ki-Hyeok; Lee, Do W; Yi, Chae S (2010) Chelate-Assisted Oxidative Coupling Reaction of Arylamides and Unactivated Alkenes: Mechanistic Evidence for Vinyl C-H Bond Activation Promoted by an Electrophilic Ruthenium-Hydride Catalyst. Organometallics 29:5748-5750
Yi, Chae S; Gao, Ruili (2009) Scope and Mechanistic Investigations on the Solvent-Controlled Regio- and Stereoselective Formation of Enol Esters from the Ruthenium-Catalyzed Coupling Reaction of Terminal Alkynes and Carboxylic Acids. Organometallics 28:6585-6592
Yi, Chae S; Lee, Do W (2009) Regioselective Intermolecular Coupling Reaction of Arylketones and Alkenes Involving C-H Bond Activation Catalyzed by an In-Situ Formed Cationic Ruthenium-Hydride Complex. Organometallics 28:4266-4268
Yi, Chae S; Lee, Do W (2009) Efficient Dehydrogenation of Amines and Carbonyl Compounds Catalyzed by a Tetranuclear Ruthenium-mu-Oxo-mu-Hydroxo-Hydride Complex. Organometallics 28:947-949

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