The synthesis of both natural and unnatural organic compounds in optically active form constitutes a central challenge in chemistry, especially in relation to the production of bioactive compounds and novel materials. In order to contribute to these studies, we invent new tools for synthesis through the design of chiral catalysts and widely applicable catalytic strategies to effect chemo- and stereoselective transformations. Our research aims to elucidate reactivity principles of organic and organometallic catalysis and to reduce the environmental impact of synthetic organic chemistry through the identification of practical and efficient methods.
The problems that we choose to address provide routes to complex organic architectures from readily available and inexpensive feedstock chemicals. In the past year, we have pursued three areas within this program: (1) the invention of new catalytic reaction methods for the synthesis of fluorinated compounds using nucleophilic fluorine sources; (2) the development of transition metal-catalyzed C–C bond-forming reactions with epoxides, aziridines, and N-containing aromatic compounds; and (3) the design of chiral hemilabile phosphine ligands of broad utility for enantioselective catalysis.
Projects in the group are designed to provide students with expertise in reaction discovery and development, while exposing them to problems in complex target synthesis and mechanistic analysis.
Selected Recent Publications
- Kalow, J. A.; Doyle, A. G. Enantioselective Ring-Opening of Epoxides by Fluoride Anion Promoted by a Cooperative Dual Catalyst System. J. Am. Chem. Soc. 2010, 132, 3268-326
- McLaughlin, M.; Garcia Rubio, S.; Wilson, I.; Zhao, W.; Laird, T.; Zlota, A. Some Items of Interest to Process R&D Chemists and Engineers. Org. Proc. Res. Dev. 2010, 14, 750–758.
- Asymmetric Synthesis of Fluorohydrins. Synfacts 2010, 673.
- Enantioselective Ring Opening of Epoxides by Fluoride Anion. Synform 2010, A58.
- Reisman, S. E.; Doyle, A. G.; Jacobsen, E. N. Enantioselective Thiourea-Catalyzed Additions to Oxocarbenium Ions. J. Am. Chem. Soc. 2008, 130, 7198-7199.
- Doyle, A. G.; Jacobsen, E. N. Small-Molecule H-Bond Donors in Asymmetric Catalysis. Chem. Rev. 2007, 107, 5713-5743.
- Doyle, A. G.; Jacobsen, E. N. Enantioselective Alkylation of Acyclic α,α-Disubstituted Tributyltin Enolates Catalyzed by a Cr(salen) Complex. Angew. Chem. Int. Ed. 2007, 46, 3701-3705.
- Doyle, A. G.; Jacobsen, E. N. Enantioselective Alkylations of Tributyltin Enolates Catalyzed by Cr(salen)Cl: Access to Enantiomerically Enriched All-Carbon Quaternary Centers. J. Am. Chem. Soc. 2005, 127, 62-63.
- Ellsworth, B. A.; Doyle, A. G.; Patel, M.; Caceres-Cortes, J.; Meng, W.; Deshpande, P. P.; Pullockaran, A.; Washburn, W. N. C-Arylglucoside synthesis: triisopropylsilane as a selective reagent for the reduction of an anomeric C-phenyl ketal. Tetrahedron-Asymmetry 2003, 14, 3243-3247.
- White, M. C.; Doyle, A. G.; Jacobsen, E. N. A Synthetically Useful, Self-Assembling MMO Mimic System for Catalytic Alkene Epoxidation with Aqueous H2O2. J. Am. Chem. Soc. 2001, 123, 7194-7195.
- Chem. & Eng. News 2001, 79, 9.
- Chem. & Eng. News Highlights 2001, 79, 51.