- 2007 Shelby Hall
- (205) 348-4435
- (205) 348-9104
BS, 1992, University of Nebraska
Ph.D., 1998, Stanford University
Postdoctoral Associate, 1997-1999, Yale University
Metal-catalyzed organic reaction development and mechanistic study
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 the following:
- 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.
- Structure-activity relationships for ligands: The Shaughnessy group has a long-standing interest in understanding how steric and electronic properties of ligands affect catalyst performance. In collaboration with computational chemists, we try to understand how ligand design can be used to design more efficient catalyst systems.
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).
Hu, H.; Qu, F.; Gerlach, D. L.; Shaughnessy, K. H. “Mechanistic Study of the Role of Substrate Steric Effects and Aniline Inhibition on the Bis(trineopentylphosphine)-palladium(0)-Catalyzed Arylation of Aniline Derivative” ACS Catal., 2017, 7, 2516-2527.
Lauer, M. G.; Headford, B. R.; Gobble, O. M.; Weyhaupt, M. B.; Gerlach, D. L.; Zeller, M.; Shaughnessy, K. H. “A Trialkylphosphine Derived Palladacycle as a Catalyst in the Selective Cross-Dimerization of Terminal Arylacetylenes with Terminal Propargyl Alcohols and Amides” ACS Catal., 2016, 6, 5834-5842.
Semmes, J. G.; Bevans, S. L.; Mullins, C. H.; Shaughnessy, K. H. “Arylation of diethyl malonate and ethyl cyanoacetate catalyzed by palladium/di-tert-butylneopentyl-phosphine,” Tetrahedron Lett., 2015, 56, 3447-3450.
Moore, J. N.; Laskay, N. M.; Duque, K. S.; Kelley, S. P.; Rogers, R. D.; Shaughnessy, K. H. “Synthesis of 4-Sulfonatobenzylphosphines and Their Application in Aqueous-Phase Palladium-Catalyzed Cross-Coupling,” J. Organomet. Chem. 2015, 777, 16-24.
Lauer, M. G.; Thompson, M. K.; Shaughnessy, K. H. “Controlling Olefin Isomerization in the Heck Reaction with Neopentyl Phosphine Ligands,” J. Org. Chem., 2014, 79, 10837-10848.
Raders, S. M.; Jones, J. M.; Semmes, J. G.; Kelley, S. P.; Rogers, R. D; Shaughnessy, K. H. “Di-tert-butylneopentylphosphine (DTBNpP): An Efficient Ligand in the Palladium-Catalyzed α-Arylation of Ketones,” Eur. J. Org. Chem. 2014, 7395-7404.
Bhattarai, B. T. Adhikari, S.; Kimball, E. A.; Moore, J. N.; Shaughnessy, K. H.; Snowden, T. S.; Fronczek, F. R.; Dolliver, D. D. “Palladium-catalyzed ortho-halogenation of diaryl oxime ethers,” Tetrahedron Lett. 2014, 55, 4801-4806.
Raders, S. M.; Moore, J. N.; Parks, J. K.; Miller, A. D.; Leißing, T. M.; Kelley, S. P.; Rogers, R. D.; Shaughnessy, K. H., “Trineopentylphosphine: A Conformationally Flexible Ligand for the Coupling of Sterically Demanding Substrates in the Buchwald-Hartwig Amination and Suzuki-Miyaura Reaction,” J. Org. Chem., 2013, 78, 4649-4664.
Dolliver, D. D.; Bhattarai, B. T.; 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., “Stereospecific Suzuki, Sonogashira, and Negishi coupling reactions of N-alkoxyimidoyl iodides and bromides,” J. Org. Chem, 2013, 78, 3676-3687.
Shaughnessy, K. H. “Hydrophilic Ligands and Their Application in Aqueous-Phase Metal-Catalyzed Reactions,” Chem. Rev., 2009, 109, 643-710.