The long term goal of this research is to study synthetic and mechanistic aspects of metal-catalyzed C-H and N-H bond activation reactions. Transition metal-catalyzed C-H and N-H bond activation reactions are powerful synthetic methods for forming a wide variety of natural products and pharmaceutical agents. For example, transition metal-catalyzed C-H bond activation reaction can directly introduce heteroatom functional groups to unreactive hydrocarbons under environmentally benign conditions. Transition metal-catalyzed hydroamination reaction is a highly effective method for forming amine compounds in an atom-economical fashion. Furthermore, asymmetric version of the hydroamination reaction has high potential for stereoselective formation of nitrogen compounds. The paramount challenge for these catalytic reactions is to design metal catalysts which are applicable to the synthesis of a variety of natural products and pharmaceutical agents. The major objective of the proposed research is to study the synthetic and mechanistic aspects of the ruthenium-catalyzed C-H bond activation of amines and hydroamination reactions. This research seeks to gain the reaction mechanisms for catalytic C-H bond activation of amines and hydroamination of alkenes by employing well-defined ruthenium complexes. The proposed research will provide new catalytic methods for the synthesis of anticancer drugs and anti-inflammatory agents. ? ? ?

Agency
National Institute of Health (NIH)
Institute
National Institute of General Medical Sciences (NIGMS)
Type
Academic Research Enhancement Awards (AREA) (R15)
Project #
2R15GM055987-05A1
Application #
7125799
Study Section
Special Emphasis Panel (ZRG1-BCMB-R (90))
Program Officer
Schwab, John M
Project Start
1998-08-01
Project End
2010-07-31
Budget Start
2006-08-01
Budget End
2010-07-31
Support Year
5
Fiscal Year
2006
Total Cost
$220,500
Indirect Cost
Name
Marquette University
Department
Chemistry
Type
Schools of Arts and Sciences
DUNS #
046929621
City
Milwaukee
State
WI
Country
United States
Zip Code
53201
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
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
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; 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

Showing the most recent 10 out of 17 publications