KEVIN H. SHAUGHNESSY Associate Professor and Chair 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: 2072 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. We are particularly interested in the design of ligands to promote interesting metal-catalyzed transformations. Our efforts in ligand design focus on trying to understand the role of steric and electronic ligand properties on catalytic processes. Another area of general interest is the design of sustainable metal-catalyzed synthetic processes. Areas of current interest 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. Water soluble ligands also provide the opportunity to functionalize hydrophilic biomolecules under homogeneous conditions.
• Novel ligand architectures for metal-catalyzed reactions: A current area of interest is the exploration of phosphine ligands with conformationally flexible substituents, such as neopentyl, in metal-catalyzed cross-coupling reactions. Steric bulk is a critical requirement for many late transition metal-catalyzed reactions. We have found that ligands with conformationally flexible steric demand can provide catalysts with broad substrate scope, including sterically demanding substrates.
• Catalysis applications in sustainable chemistry: Catalysis will play an important role in a sustainable future. Development of more atom-efficient synthetic methods is one area of need. Direct functionalization of C-H bonds, rather than more highly functionalized substrates is an important area of development. Future energy sources will require new types of chemistry to be realized. Our group is interested in developing catalysts for applications in biomass utilization and energy storage.

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

"Trineopentylphosphine: A Conformationally Flexible Ligand for the Coupling of Sterically Demanding Substrates in the Buchwald-Hartwig Amination and Suzuki-Miyaura Reaction," Raders, S. M.; Moore, J. N.; Parks, J. K.; Miller, A. D.; Leißing, T. M.; Kelley, S. P.; Rogers, R. D.; Shaughnessy, K. H. J. Org. Chem., 2013, 4649-4664.

"Stereospecific Suzuki, Sonogashira, and Negishi Coupling Reactions of N-Alkoxyimidoyl Iodides and Bromides," Dolliver, D. D.; Bhattarai, B.; Pandey, A.; Lanier, M. L.; Bordelon, A. S.; Adhikari, S.; Dinser, J. A.; Flowers, P. F.; Wills, V. S.; Schneider, C. L.; Shaughnessy, K. H.; Moore, J. N.; Raders, S. M.; Snowden, T. S.; McKim, A. S.; Fronczek, F. R.J. Org. Chem, 2013, 3676-3687.

"Aqueous-phase Sonogashira alkynylation to synthesize 5-substituted pyrimidine and 8-substituted purine nucleosides," Cho, J. H.; Shaughnessy, K. H. Curr. Prot. Nucleic Acid Chem. 2012, 49, 1.27.1-10.

"Aqueous-Phase Heck Coupling of 5-Iodouridine and Alkenes under Phosphine-Free Conditions." Cho, J. H.; Shaughnessy, K. H. Synlett 2011, 2963-2966.

"Synthesis and X-ray Structure Determination of Highly Active Pd(II), Pd(I), and Pd(0) Complexes of Di(tert-butyl)neopentylphosphine (DTBNpP) in the Arylation of Amines and Ketones,"Hill, L. L.; Crowell, J. L.; Tutwiler, S. L., Massie, N. L., Hines, C. C.; Griffin, S. T.; Rogers, R. D.; Shaughnessy, K. H.; Grasa, G. A.; Johansson Seechurn, C. C. C.; Li, H.; Colacot, T. J.; Chou, J.; Woltermann, C. J. J. Org. Chem. 2010, 75, 6477–6488.

"Efficient Sonogashira Coupling of Unprotected Halonucleosides in Aqueous Solvents Using Water-Soluble Palladium Catalysts," Cho, J. H.; Prickett, C. D.; Shaughnessy, K. H. Eur. J. Org. Chem. 2010, 3678-3683.

"Hydrophilic Ligands and Their Application in Aqueous-Phase Metal-Catalyzed Reactions," Shaughnessy, K. H. Chem. Rev, 2009, 109,643-710.

"Sterically-Demanding, Zwitterionic Trialkylphosphonium Sulfonates as Air-Stable Ligand Precursors for Efficient Palladium-Catalyzed Cross-Couplings of Aryl Bromides and Chlorides," Brown, W. S.; Boykin, D. D.; Sonnier, M. Q., Jr.; Clark, W. D.; Brown, F. V.; Shaughnessy, K. H. Synthesis, 2008, 1965-1970.

"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).

Complete list of Dr. Shaughnessy's publications (5/17/13)

The University of Alabama Department of Chemistry Faculty