Asymmetric catalysis with metal carbenes and Lewis acids; structural design and chemistry of dirhodium carboxamidates; catalytic chemical oxidations; bioinorganic chemistry of nitrogen oxides and nitrosyls; reductions by organosilanes.
American Chemical Society (ACS), Fellow; American Association for the Advancement of Science (AAAS) Fellow; Royal Society of Chemistry, Fellow
Major Recognitions and Honors
Significant Professional Service and Activities
American Chemical Society: President, Chemical Society of Washington (2011); Executive Committee for the Division of Organic Chemistry (1988-present), ACS Councilor (1990-2011, elected office), Division Chairman (1993); Chairman, Joint Board-Council Committee on Publications (1997-1999); Chair, Editorial Board for C&E News (1997-1999); Committee on Science (1995-2003); Committee on Committees (1996-98, elected by Council); Committee on Nominations and Elections (2002-2007, elected by Council); Board Task Force on Minorities (1991-92); Chairman, Membership Affairs Committee (1990-1992); Board of Trustees, Group Insurance Plans (1990-1992). International Union of Pure and Applied Chemistry: Titular Member and Secretary, Commission on Physical Organic Chemistry (III.2), 1987-91. National Research Council: Chemical Sciences Roundtable (2000-2004) and member of its Executive Committee; Co-organizer, CSR Workshop and Report on “Preparing Chemists and Chemical Engineers for a Globally Oriented Workforce” (October 2003); Board on Chemical Sciences and Technology (1990-1994); Committee on Undergraduate Science Education (1993-96). Council for Chemical Research: Member, Board of Directors (2008-2010); Executive Committee (2009-2010). Council on Undergraduate Research: Founding Member, First President (1978-1983), and Editor of the CUR Newsletter (1978-1993).National Conferences on Undergraduate Research: Founding Member and first Chairman (1985-1988). Foundations: Research Corporation – Board of Directors (1989-1997, 2000-2002), Cottrell Program Advisory Committee (1978-83); Camille and Henry Dreyfus Foundation – Foundation Advisor, (1989-1997); National Institutes of Health - SBCA Study Section (2003-2007), NIGMS Council (ad hoc, 1992, 2001); National Science Foundation - Committee of Visitors, Division of Chemistry (2010). Journals: current Editorial Boards: Acc. of Chem. Res., Organic Letters, Russian Chemical Bulletin, The Chemical Record.
To date 147 undergraduate students are coauthors of research publications with Doyle, 60 of whom have received their Ph.D. in the chemical sciences; 46 Postdoctoral Associates; and, only since 2003, 9 students received Ph.D. degrees and 2 students received M.S. degrees.
Michael P. Doyle: Dirodium Carboxamidates in Catalysis and Materials
The major focus of our research program is the development of highly selective and efficient catalytic processes for the synthesis of biologically relevant compounds. Investigations are built upon unique, highly efficient and selective, catalytic uses of dirhodium carboxamidates. The fixed stereodefined geometry of these catalysts provides access to highly enantioenriched products in metal carbene reactions of diazoacetates and, together with their low oxidation potentials, also provides capabilities for highly selective Lewis acid catalyzed reactions and efficient chemical oxidations with high turnover numbers and high selectivities. (See: “Catalytic Carbene Insertion into C-H Bonds,” Chem. Rev., 2010, 110, 704-724.). We are developing diazo chemistry for catalytic stereoselective transformations to further enhance applicability of catalytic metal carbene chemistry in organic synthesis. New catalytic syntheses of multi-functional β-keto-α-diazoesters with subsequent catalytic transformations provide highly efficient access to more complex carbon frameworks than previously possible through reactions with diazocarbonyl compounds. Enoldiazoacetates provide a rich framework for a variety of molecular constructions (see “Rhodium(II) and Copper(II) Catalyzed Reactions and Michael P. of Enoldiazoacetates with Nitrones. Metal Carbene versus Lewis Acid Directed Pathways” Angew. Chem. Int. Ed. 2012, 51, 5900-5903 and “Highly Regio- and Stereoselective Dirhodium Vinylcarbene-induced Nitrone Cycloaddition with Subsequent Cascade Carbenoid Aromatic Cycloaddition/N-O Cleavage and Rearrangement” Angew. Chem. Int. Ed. 2012, 51, 5907-5910).
Lewis acidic chiral dirhodium(II,III) carboxamidate catalysts are being used to broaden the range of asymmetric Lewis acid catalyzed carbon-carbon bond forming transformations. Reactivity and selectivity enhancement through chiral Rh25+ catalysts expands their utilization to Lewis acid catalyzed reactions for which chiral Rh24+ catalysts are ineffective. (See: “Solvent Enhancement of Reaction Selectivity: A Unique Property of Cationic Chiral Dirhodium Carboxamidates” J. Am. Chem. Soc. 2011, 133, 9572-9579 and “Asymmetric Formal [3+3] Cycloaddition Reactions of Nitrones with Electrophilic Vinylcarbene Intermediates” J. Am. Chem. Soc. 2011, 133, 16402-16405).
Catalytic oxidative methodologies to prepare compounds that are of biological significance are being developed. Newly discovered tert-butyl hydroperoxide oxidations catalyzed by dirhodium caprolactamate, based in large part on its low oxidation potential and solubility in water and organic solvents, offer a unique opportunity to develop a spectrum of oxidative transformations, compatible with water as a solvent, that are not easily achieved by other methods (especially allylic and benzylic oxidations). Applications encompass reactions with steroids, phenolic compounds, unsaturated fatty acid derivatives, terpenes, amines, and other biologically relevant substrates. (See: “Dirhodium-Catalyzed Phenol and Aniline Oxidations with T-HYDRO. Substrate Scope and Mechanism of Oxidation” J. Org. Chem. 2011, 73, 2585-2593).