KEVIN H. SHAUGHNESSY Associate Professor and Director of Undergraduate Studies ORGANIC/ORGANOMETALLIC CHEMISTRY Metal-catalyzed organic synthetic methodology, Environmentally benign reactions, High-throughput screening of reaction selectivity BS, 1992, University of Nebraska; Ph.D., 1998, Stanford University; Postdoctoral Associate, 1997-1999, Yale University office: 232 Shelby Hall Telephone: (205) 348-4435 FAX (205) 348-9104 Shaughnessy Group Home Page Affiliation: Center for Green Manufacturing

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Research Interests

Research in the Shaughnessy group focuses on organometallic chemistry. One of the most interesting and important applications of organometallic complexes is as catalysts in organic synthesis. Therefore our efforts are focused on understanding organometallic reaction mechanisms that are relevant to important catalytic systems. By understanding the mechanism by which organometallic species catalyze important transformations, we can develop new or improved synthetic methodologies. Much of our research focuses on the use of alternative solvents in catalysis in an effort to develop more environmentally benign catalytic processes. Current research efforts in the group include:

• Development of novel ligands for aqueous-phase catalysis: Water is an attractive environmentally benign solvent. We are interested in designing new ligands that will provide efficient, water-soluble catalysts for organic reactions. We have developed a family of water-soluble phosphines that provide efficient catalysts for palladium-catalyzed cross-coupling reactions in aqueous-solvents. Current efforts are focused at understanding the coordination chemistry of these ligands and designing the next generation of ligands that will provide improved catalyst performance.
• Biomolecule modification using water-soluble catalysts: We are interested in applying water-soluble catalysts developed by us to the modification of hydrophilic biomolecules, such as nucleosides, nucleic acids, proteins, and carbohydrates. We have found that water-soluble arylphosphines provide active catalysts for the arylation of halogenated nucleosides in aqueous solvents. In this way we can prepare arylated nucleosides that are important models for carcinogenesis studies and potential pharmaceuticals.
• Ionic liquids as novel solvents in catalysis: Ionic liquids, salts that are liquid at room temperature, have a number of unique properties that make them potentially attractive solvents for catalytic reactions. We are interested studying the effect of ionic liquid structure on fundamental organometallic reactions. We have also shown that ionic liquids are good solvents for palladium-catalyzed olefin/carbon monoxide copolymerizations.

Students in the Shaughnessy group gain experience in a wide range of synthetic techniques for organic and organometallic synthesis as well as experience with a variety of spectroscopic techniques (i.e., NMR, IR, UV/Visible, and Mass spectroscopy, as well as X-ray crystallography).

Representative Publications

"Neopentylphosphines as Effective Ligands in Palladium-Catalyzed Cross-Couplings of Aryl Bromides and Chlorides," Hill, L. L.; Smith, J. M.; Brown, W. S.; Moore, L. R.; Guevara, P.: Pair, E. S.; Porter, J.; Chou, J.; Wolterman, C. J.; Craciun, R.; Dixon, D. A.; Shaughnessy, K. H. Tetrahedron, 64, 6920-6934 (2008)

"Sterically Demanding, Sulfonated, Triarylphosphines:  Application to Palladium-Catalyzed Cross-Coupling, Steric and Electronic Properties, and Coordination Chemistry," Moore, L. R.; Western, E. C.; Craciun, R.; Spruell, J. M.; Dixon, D. A.; O'Halloran, K. P.; Shaughnessy, K. H. Organometallics, 27, 576-593 (2008).

"Synthesis and Characterization of Water-Soluble Silver and Palladium Imidazol-2-ylidene Complexes with Non-Coordinated Anionic Substituents, " Moore, L. R.; Cooks, S. M; Anderson, M. S.; Schanz, H.-J.; Griffin, S. T.; Rogers, R. D.; Kirk, M. C; Shaughnessy, K. H. Organometallics, 25, 5151-5158 (2006).

"Water-Soluble Palladacycles as Precursors to Highly Recyclable Catalysts for the Suzuki Coupling of Aryl Bromides in Aqueous Solvents," Huang, R. and Shaughnessy, K. H. Organometallics, 25, 4105-4112 (2006).

"Beyond TPPTS: New Approaches to the Development of Efficient Palladium-Catalyzed Aqueous-Phase Cross-Coupling Reactions," Kevin H. Shaughnessy, Eur. J. Org. Chem., 1827-1835 (2006) . Cover Artwork.

"Inhibitory Effects of the Guanine Moiety on Suzuki Couplings of Unprotected Halonucleosides in Aqueous Media," Western, E. C.; Shaughnessy, K. H., J. Org. Chem., 70,3678-3688 (2005).

"Promoting Effect of Ionic Liquids on Ligand Substitution Reactions." Sliger, M. D.; Traylor, R. K.; McNeill, J., III; Young, S. H.; Hoffman, N. W.; Klingshirn, M. A.; Rogers, R. D.; and Shaughnessy, K. H. J. Organomet. Chem. 69,0 3540-3545 (2005).

"Steric and Electronic Effects on the Coordination of Sterically Demanding, Water-Soluble Alkylphosphines to Palladium under Reducing Conditions: Correlation to Catalytic Activity." DeVasher, R. B.; Spruell, J. M.; Dixon, D. A.; Broker, G. A.; Griffin, S. T.; Rogers, R. D.; Shaughnessy, K. H. Organometallics 24, 962-971 (2005).

"Aqueous-Phase, Palladium-Catalyzed Cross-Couplings of Aryl Bromides Under Mild Conditions Using Water-Soluble, Sterically Demanding Alkylphosphines." DeVasher, R. B.; Moore, L. R.; Shaughnessy, K. H. J. Org. Chem. 69, 7919-7927 (2004).

"Efficient One-Step Suzuki Arylation of Unprotected Halonucleosides using Water-Soluble Palladium Catalysts,” Western, E. C.; Daft, J. R.; Johnson, E. M., II; Gannett, P. M.; Shaughnessy, K. H. J. Org. Chem., 68, 6767-6774 (2003).

Complete list of Dr. Shaughnessy's publications (7/3/08)

The University of Alabama Department of Chemistry Faculty