The long term objectives of this research are to achieve both detailed mechanistic understandings and to develop new synthetic methods for a number of different alkyne coupling reactions. Transition metal- catalyzed alkyne coupling reactions have been extensively utilized in the synthesis of a wide range of natural products. Transition metal sigma-acetylide complexes are considered to be important intermediate species in some of these reactions. This research proposes to study the fundamental reactivity of coordinatively unsaturated ruthenium-acetylide complexes toward the coupling reactions of alkynes with alkenes and carbonyl compounds. This research proposes to examine the mechanisms of these alkyne coupling reactions. Specific plans are presented to explore the catalytic activity of unsaturated ruthenium-acetylide species in these reactions. Metallacyclopentadiene complexes have been widely implicated as key intermediate species in a number of different alkyne oligomerization reactions. The newly formed ruthenacyclopentadiene complex was shown to catalyze the linear coupling reactions of acetylenes and olefins. The proposal describes specific plans to study the reactivity and catalytic activity of the ruthenacyclopentadiene complexes towards linear alkyne coupling reactions. The specific goals of this research are to study the fundamental reactivity and catalytic activity of the ruthenium-acetylide and ruthenacyclopentadiene complexes toward the alkyne coupling reactions, and to establish the detailed mechanisms of these reactions.

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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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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