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Department of Chemistry & Biochemistry
The University of Texas at Austin
1 University Station A5300
Austin, TX 78712-0165
Contact Information
Office: WEL: 5.208
Phone: 232-5892
Lab
Office: WEL 5.204
Phone: 471-5955
Fax: 471-8696
Michael J. Krische
mkrische@mail.utexas.edu
Professor, Faculty
Environmental Science Institute
Director, Center for Green Chemistry and Catalysis
Robert A. Welch Chair in Science
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Research GroupThe Krische Group |
EducationBS, University of California Berkley, 1989 Fulbright Fellowship, Helsinki University, 1990 PhD, Stanford University, 1996 Postdoctoral Studies, Universite' Louis Pasteur 1999 |
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AwardsMukaiyama Award, 2010 Humboldt Research Award, 2009 Tetrahedron Young Investigator Award, 2009 Novartis Lectureship Award, 2008 Presidential Green Chemistry Award, 2007 Dowpharma Prize, 2007 Elias J. Corey Award, 2007 Solvias Ligand Prize, 2006 Johnson & Johnson Focused Giving Award, 2005 Japanese Society of Synthetic Chemistry, Lectureship on Organic Synthesis, 2005 Camille Dreyfus Teacher Scholar Award, 2003 Alfred P. Sloan Research Fellowship, 2003 Cottrell Scholar Award, 2002 Lilly Grantee Award, 2002 Frasch Foundation Award in Chemistry, 2002 National Science Foundation-CAREER Award, 2000 NIH Post-Doctoral Fellow, 1997 Peter Veatch Fellow, 1995 Sigma Xi Fellow, 1990 Fulbright Fellow, 1990 Presidents Undergraduate Fellow, 1989 |
Affiliations
Center for Nano- and Molecular Science and Technology; Texas Materials Institute; Environmental Science Institute;
Natural Product Synthesis, Catalytic Reaction Development, Organometallic Chemistry and Self-Assembly
Our research focuses on catalytic reaction development with attendant applications in natural product synthesis. A central theme involves the identification of new reactivity patterns, the evolution of related catalytic processes and, ultimately, the development of new synthetic strategies. Specific areas of research include: (a) hydrogen-mediated C-C bond formation, (b) nucleophilic catalysis via phosphine conjugate addition, (c) catalytic tandem conjugate addition-electrophilic trapping, and (d) metal-catalyzed [2+2]cycloaddition.
H2-Mediated C-C Bond Formation: The formation of carbon-carbon (C-C) bonds is of fundamental significance. Research in the Krische laboratory demonstrates that C-C bond formation may be achieved under the conditions of catalytic hydrogenation and transfer hydrogenation. These studies represent the first systematic efforts to exploit hydrogenation in C-C couplings beyond hydroformylation and define a departure from the use of preformed organometallic reagents in carbonyl addition.
The Krische group reports that diverse π-unsaturated reactants reductively couple to carbonyl compounds and imines under hydrogenation conditions, thereby providing a byproduct-free alternative to stoichiometrically preformed organometallic reagents in a range of classical C=X (X = O, NR) addition processes. In such transformations, one simply hydrogenates two molecules in the presence of one another to form a single more complex product. This work evokes the question of whether all processes employing stoichiometric metallic reagents can be conducted catalytically under hydrogenative conditions.
More recently, by exploiting alcohols as both hydrogen donors and aldehyde precursors, byproduct-free carbonyl addition is achieved from the alcohol oxidation level. Such alcohol-unsaturate C-C couplings circumvent the redox manipulations often required to convert alcohols to aldehydes, and again bypass the barriers imposed by the use of stoichiometrically preformed organometallics. As chemical industry shifts from petrochemicals to renewable feedstocks, such direct byproduct-free couplings of alcohols are anticipated to find broad use
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Representative Publications
Kim, I. S.; Ngai, M.-Y.; Krische, M. J. "Enantioselective Iridium Catalyzed Carbonyl Allylation from the Alcohol or Aldehyde Oxidation Level Using Allyl Acetate as an Allyl Metal Surrogate," J. Am. Chem. Soc. 130 (2008): 6340.
Patman, R. L.; Williams, V. M.; Bower, J. F.; Krische, M. J. "Carbonyl Propargylation from the Alcohol or Aldehyde Oxidation Level Employing 1,3-Enynes as Surrogates to Preformed Allenylmetal Reagents: A Ruthenium Catalyzed C-C Bond Forming Transfer Hydrogenation," Angew. Chem. Int. 47 (2008): 5220.
Bee, C.; Han, S. B.; Hassan, A.; Iida, H.; Krische, M. J. "Diastereo- and Enantioselective Hydrogenative Aldol Coupling of Vinyl Ketones: Design of Effective Monodentate TADDOL-Like Phosphonite Ligands," J. Am. Chem. Soc 130 (2008): 2747.
Barchuk, A.; Ngai, M.-Y.; Krische, M. J. "Enantioselective Iridium Catalyzed Imine Vinylation: Optically Enriched Allylic Amines via Alkyne-Imine Reductive Coupling Mediated by Hydrogen" J. Am. Chem. Soc. 129 (2007): 12644.
Skucas, E.; Kong, J.-R.; Krische, M. J. "Enantioselective Reductive Coupling of Acetylene to N-Arylsulfonyl Imines via Rhodium Catalyzed C-C Bond Forming Hydrogenation: (Z)-Dienyl Allylic Amines" J. Am. Chem. Soc. 129 (2007): 7242.