Contact InformationOffice: WEL: 5.208
LabOffice: WEL 5.204
Michael J. Krischemkrische@cm.utexas.edu
Environmental Science Institute
Director, Center for Green Chemistry and Catalysis
Robert A. Welch Chair in Science
BS, University of California Berkley, 1989
Fulbright Fellowship, Helsinki University, 1990
PhD, Stanford University, 1996
Postdoctoral Studies, Universite' Louis Pasteur 1999
JSPS Fellow, 2013
ACS Cope Scholar Award, 2013
GlaxoSmithKline Scholar Award, 2011
Mukaiyama 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
Transition Metal Catalysis, Natural Product Synthesis, Organometallic and Green Chemistry
Reactions that form carbon-carbon bonds are of fundamental importance to the endeavor of chemical synthesis. The largest volume application of homogenous metal catalyzed C-C coupling is alkene hydroformylation, which may be viewed as the prototypical C-C bond forming hydrogenation. Our laboratory is engaged in the first systematic efforts to develop C-C bond forming hydrogenations beyond hydroformylation - processes wherein two or more reactants are hydrogenated to form a single, more complex product. Using cationic rhodium and iridium catalysts, we have found that diverse π-unsaturated reactants reductively couple to carbonyl compounds and imines under hydrogenation conditions, offering a byproduct-free alternative to stoichiometric organometallics in a range of classical C=X (X = O, NR) addition processes. This concept is extended further via “C-C bond forming transfer hydrogenation”. In such processes, the exchange of hydrogen between alcohols and unsaturated reactants serves to generate aldehyde-organometal pairs that combine to give products of carbonyl addition or hydrohydroxyalkylation. Direct alcohol CH-functionalization in this manner is again byproduct-free, and avoids discrete redox manipulations often required to convert alcohols to aldehydes. Using these merged redox-C-C bond construction events, total syntheses of 6-deoxyerythronolide B, bryostatin 7, cyanolide A and roxaticin, and formal syntheses of rifamycin S and scytophycin C, were accomplished. These syntheses are the most concise routes reported, to date, to any member of these natural products families. More broadly, this body of work evokes question of whether all processes that now rely upon premetallated reagents can be conducted catalytically under hydrogenation or transfer hydrogenation conditions in the absence of stoichiometric organometallics.
Geary, L. M.; Glasspoole, B. W.; Kim, M. M. Krische, M. J. “Successive C-C Coupling of Dienes to Vicinally Dioxygenated Hydrocarbons: Ruthenium Catalyzed [4+2] Cycloaddition across the Diol, Hydroxycarbonyl or Dione Oxidation Levels,” J. Am. Chem. Soc. 135 (2013): 3796.
Gao, X.; Woo, S. K.; Krische, M. J. “Total Synthesis of 6-Deoxyerythronolide B via C-C Bond-Forming Transfer Hydrogenation,” J. Am. Chem. Soc. 135 (2013): 4223.
Dechert-Schmitt, A.-M. R.; Schmitt, D. C.; Krische, M. J. “Site-Selective Primary Alcohol Dehydrogenation Enables Protecting Group-Free Diastereoselective C-C Coupling of 1,3-Glycols and Allyl Acetate,” Angew. Chem. Int. Ed. 52 (2013): 3195.
Zbieg, J. R.; Yamaguchi, E.; McInturff, E. L.; Krische, M. J. “Enantioselective C-H Crotylation of Primary Alcohols via Hydrohydroxyalkylation of Butadiene,” Science 336 (2012): 324.
Lu, Y.; Woo, S. K.; Krische, M. J. “Total Synthesis of Bryostatin 7 via C-C Bond Forming Hydrogenation,” J. Am. Chem. Soc. 132 (2011): 13876.