Room: 8108
Phone: 608-265-2261
Email: schomakerj@chem.wisc.edu
Position: Assistant Professor
B. Borhan, J.M. Schomaker, S. Bhattacharjee, and K. Korthals, "Synthesis of N-Heterocycles, b-Amino Acids, and Allyl Amines via Aza-Payne Mediated Reaction of Ylides and Hydroxy Aziridines." U.S. Pat. Appl. Publ. 2009, US 20090012120. J.M. Schomaker and B. Borhan, "Total Syntheses of Haterumalides NA and NC via a Chromium-Mediated Macrocyclization." J. Am. Chem. Soc. 2008, 130, 12228-12229.
J.M. Schomaker, W.C. Boyd, I.C. Stewart, F.D. Toste, and R.G. Bergman, "Cobalt Dinitrosoalkane Complexes in the C-H Functionalization of Olefins." J. Am. Chem. Soc. 2008, 130, 3777-3779.
J.M. Schomaker, A.R. Geiser, R. Huang, and B. Borhan, "Tetrasubstituted Pyrrolidines via a Tandem Aza-Payne/Hydroamination Reaction." J. Am. Chem. Soc., 2007, 129, 3794-3795.
J.M. Schomaker, S. Bhattacharjee, J. Yan, and B. Borhan, "Diastereomerically and Enantiomerically Pure 2,3-Disubstituted Pyrrolidines from 2,3-Aziridin-1-ols Using a Sulfoxonium Ylide: A One-Carbon Homologative Relay Ring Expansion." J. Am. Chem. Soc., 2007, 129, 1996-2003.
J.M. Schomaker, S. Bhattacharjee, J. Yan, and B. Borhan, "Diastereomerically and Enantiomerically Pure 2,3-Disubstituted Pyrrolidines from 2,3-Aziridin-1-ols Using a Sulfoxonium Ylide: A One-Carbon Homologative Relay Ring Expansion." J. Am. Chem. Soc., 2007, 129, 1996-2003. T.J. Delia, J.M. Schomaker, and A. Kalinda, "The Synthesis of Substituted Phenylpyrimidines via Suzuki Coupling Reactions." J. Heterocyclic Chem. 2006, 43, 127-131.
T. Zheng, R.S. Narayan, J.M. Schomaker, and B. Borhan, "One-Pot Regio- and Stereoselective Cyclization of 1, 2,n-triols." J. Am. Chem. Soc. 2005, 127, 6946-6947.
J.M. Schomaker, V.R. Pulgam, B. Borhan, "Synthesis of Diastereomerically and Enantiomerically Pure Substituted Tetrahydrofurans Using a Sulfoxonium Ylide." J. Am. Chem. Soc. 2004, 126, 13600-13601.
J.M. Schomaker, and B. Borhan, "Total Synthesis of (+)-Tanikolide Via Oxidative Lactonization." Org. and Biomol. Chem. 2004, 2, 621-624.
B. Borhan, B.R. Travis, and J.M. Schomaker, "Catalytic Osmium-assisted Oxidative Cleavage of Olefins Using Peroxymonosulfuric Acid and Salts Thereof." U.S. Pat. Appl. Publ. 2003, US 2003149299.
| Research Description
Research Interests
 Research in the Schomaker group is driven by the need for more efficient methods to transform simple hydrocarbons into more complex building blocks for synthesis. Our program will encompass new catalyst development and optimization, elucidation of reaction mechanisms and applications of new methodologies to the synthesis of natural products and other useful molecules. Particular emphasis will be placed on the design of catalysts that can utilize environmentally friendly oxidants, such as oxygen and carbon dioxide. The potential applications of our new catalysts to industrially important transformations will also be explored.
New Methods for Polyamination
Polyamines are important components of many pharmaceuticals and biologically active molecules. They can be utilized as probes for the study of disease pathways, function as small molecule RNA inhibitors, serve as ligands for transition-metal asymmetric catalysis or act as chelates for metals in biomedical or environmental applications. New methods for the preparation of 1,2-diamines have recently been reported; however, good general and efficient methods to install multiple C-N bonds or to access highly substituted polyamines in enantioenriched form are limited. Projects in this area will focus on the development of new catalysts and oxidants capable of installing multiple C-N bonds in a single step, the construction and ring-expansion reactions of unusual strained heterocycles and the design of general methods for the preparation and use of aziridinyl amines as building blocks for synthesis.
Development of New Catalysts for Oxidative Cyclization Reactions
 The oxidative cyclizations of 1,5- and 1,6-dienes are well-known, but the analogous cyclizations of 1,3- and 1,4-dienes are plagued by oxidative cleavage and by-product formation. As 1,4-dienes are a recurring structural motif in polyunsaturated fatty acids (a renewable hydrocarbon source), new methods that can utilize these sources as building blocks for synthesis are highly desirable. Our group will model and develop new catalysts containing multiple metal centers in attempts to control the selectivity and reactivity in oxidative transformations of these substrates to useful heterocyclic rings.
 The cyclotrimerization of alkynes to yield substituted benzenes is well-precedented, although mixtures of regioisomers are often encountered when the reaction is performed in an intermolecular fashion. In contrast, the selective 2 + 2 + 2 dehydrogenative coupling of alkenes to yield aromatic rings remains an unaccomplished goal. Initial research in this area will focus on developing catalysts that can selectively cross-couple two alkenes via C-H activation, with the eventual goal of promoting selective cyclotrimerization of alkenes and/or imines to give substituted benzenes and pyridines.
New Metal Complexes Exhibiting Ligand-Based Reactivity
 Although many metal-catalyzed reactions occur by the direct interaction of the metal center with the substrate, other transition metal-mediated transformations are controlled by the interaction of the metal ligand with the substrate. A classic example of ligand-mediated reactivity is the OsO4-catalyzed dihydroxylation reaction, but the formation of C-H, C-P, C-N and C-C bonds have also been described. Studies in this area will center on the design and utilization of catalysts with ligand-based reactivity to uncover new ways to construct carbon-carbon and carbon-heteroatom bonds from a variety of unsaturated substrates. Particular emphasis will be placed on activating small molecules such as CO, CO2 and N2O towards reaction with unsaturated substrates.
Total Synthesis of Natural Products
The total synthesis of natural products offers students a chance to develop strategic and tactical expertise in the construction of complex molecules, skills that will serve them well throughout their entire scientific careers. Obviously, interesting molecular architectures and the ability to stimulate new reaction development and highlight existing reaction methodologies are valid reasons for choosing a target. In addition, total synthesis of natural products that possess specific or unusual bioactivity can provide material for collaborative projects aimed at studying the mechanism of action of these molecules and lead to the development of more effective analogues. Ruth L. Kirschstein National Research Service Award Research Training Grant (NIH) 2007-2009 American Chemical Society, Division of Organic Chemistry Graduate Fellowship sponsored by Eli Lilly 2004-2005 Michigan State University Distinguished Graduate Fellowship 2001-2005 Dow Chemical Company Foundation Graduate Fellowship 2004 Association for Women in Science Educational Foundation Predoctoral Fellowship 1999 Outstanding Thesis and Dissertation Award, Central Michigan University 1998 Dow AgroSciences Inventor Award 1997 DowElanco Inventor's Award 1993, 1994, 1996 Dow Chemical Company Special Recognition Award, Agricultural Chemicals and Process Research 1992, Organic Chemicals and Polymers 1991
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