RESEARCH OVERVIEW

Our research program focuses on the development of transition metal catalysts for applications in organic synthesis and alternative energy. Due to the importance of complex organic molecules in biology, medicine, agrochemical and material science, we are developing catalytic methods that allow high-value organic molecules to be prepared from inexpensive and abundant starting materials. We are particularly interested in inventing new reactions for the stereocontrolled introduction of heteroatoms, such as nitrogen, in rapid fashion. We are also employing principles of catalyst design and organometallic synthesis to prepare novel complexes for use as catalysts in alternative fuel preparation and energy storage. Our current efforts lie in exploring new methods for the reduction of carbon dioxide to liquid organic molecules, such as methanol, that can readily be used as fuels. Such chemistry is a potential key step in developing viable carbon-neutral fuel cycles to combat global warming and greenhouse gas emissions.

CURRENT RESEARCH New Methods for the Preparation of α-Chiral Amines α-Chiral amines are an important class of molecules encompassing a vast number of bioactive compounds and many pharmaceuticals. In addition to their use in biology, chiral amines are used as agrochemicals, as ligands for transition metals, and as resolving agents in the synthesis of fine chemicals. We are currently investigating several new enantioselective routes to this important class of compounds based upon new transition-metal catalyzed reactions.
	Bimetallic Complexes for Remote Substrate-Directed Catalysis Substrate-directed catalysis is a powerful strategy to affect both unique reactivity and high selectivity in synthetic organic chemistry. Most small molecule catalysts, however, contain only a single reactive site, which limits (by proximity) the sites on a substrate molecule that can undergo reaction in substrate-directed catalysis. We are investigating new classes of bimetallic and bifunctional catalysts, which we anticipate will greatly expand the scope of substrate-directed reactions and lead to new avenues of reactivity not previously observed with single-site catalysts.
Catalysts for the Reduction of CO2 to Methanol Wide-scale use of solar energy requires the availability of efficient, scalable energy storage; on a global scale this means developing methods to store solar energy in the form of carbon-neutral chemical fuels. We are currently investigating novel transition metal catalysts for the chemical and electrochemical reduction of carbon dioxide to methanol, a highly storable, energy-rich fuel. By deriving methanol from CO2, no net CO2 is produced when it combusted–making the overall process carbon-neutral. When solar energy is used as the energy input for the system, the overall cycle constitutes a potentially highly effective means to store solar energy.

REPRESENTATIVE PUBLICATIONS

• B. P. Fors, D. A Watson, M. R. Biscoe and S. L. Buchwald “A Highly Active Catalyst for Pd-Catalyzed Amination Reactions: Cross-Coupling Reactions Using Aryl Mesylates and the Highly Selective Monoarylation of Primary Amines Using Aryl Chlorides,” J. Am. Chem. Soc., (2008) 130, 13552.


• D. A. Watson, X. Fan and S. L. Buchwald “Carbonylation of Aryl Chlorides with Oxygen Nucleophiles at Atmospheric Pressure. Preparation of Phenyl Esters as Acyl Transfer Agents and the Direct Preparation of Alkyl Esters and Carboxylic Acids,” J. Org. Chem., (2008) 73, 7096-7101.


• J. R. Martinelli, T. P. Clark and D. A. Watson,R. H. Munday and S. L. Buchwald “Palladium-Catalyzed Aminocarbonylation of Aryl Chlorides at Atmospheric Pressure: The Dual Role of Sodium Phenoxide,” Angew. Chem. Int. Ed., (2007) 46, 8460-8463.


• L. E. Overman and D. A. Watson “Diastereoselection in the Formation of Contiguous Quaternary Carbon Stereocenters by the Intramolecular Heck Reaction,” J. Org. Chem., (2006) 71, 2600-2608.