Directory: Faculty

Matthew S. Sigman

Matthew S. Sigman

ORGANIC SYNTHESIS & ASYMMETRIC CATALYSIS

Peter J. Christine S. Stang Presidential Endowed Chair of Chemistry

B.S., Sonoma State University, 1992
Ph.D., Washington State University, 1996
NIH Postdoctoral Fellow, Harvard University, 1997-1999

Phone: (801) 585-0774

Office: 4253A HEB-N

Email: sigman@chem.utah.edu

Research Group

Biological Chemistry Program

Publications

Activities & Awards

  • Peter J. Christine S. Stang Presidential Endowed Chair of Chemistry, 2012-present
  • Fellow of the American Association for the Advancement of Science, 2011
  • U of U Distinguished Scholarly & Creative Research Award, 2011
  • Arthur C. Cope Scholar Award, 2010
  • Robert W. Parry Teaching Award, 2009
  • University of Utah Distinguished Honors Professor, 2008
  • NSF Faculty Early Career Development (CAREER) Award, 2001-2006
  • Research Innovation Award, Research Corporation, 2000-2002
  • Camille Dreyfus Teacher-Scholar Award, 2004
  • Pfizer Award for Creativity in Organic Chemistry, 2004
  • NSF Faculty Early Career Development (CAREER) Award, 2001-2006
  • Research Innovation Award, Research Corporation, 2000-2002

Research Interests

Overview. Our program is focused on the discovery of new practical catalytic reactions with broad substrate scope, excellent chemoselectivity, and high stereoselectivity to access novel medicinally relevant architectures. We believe the best strategy for developing new classes of catalysts and reactions applicable to organic synthesis is using mechanistic insight to guide the discovery process. This allows us to design new reaction motifs or catalysts in which unique bond constructions can be implemented furthering new approaches to molecule construction. An underlying theme to these methodologies is to convert relatively simple substrates into much more complex compounds allowing for access to known and novel pharmacaphores in a modular manner. This provides us the ability to readily synthesis analogs enabling us to understand the important structural features responsibility for a phenotypic response in a given biological assay. We are currently engaged in several collaborative projects to evaluate our compound collections for various cancer types at the Huntsman Cancer Institute at the University of Utah and are engaged in follow-up investigations to identify improved compounds as well as understanding the mechanism of action. For more information, please check out our WEBSITE. The group is engaged in the following diverse projects:

Pd-Catalyzed Alkene Oxidations

  • New Catalysts and Synthetic Applications for Alkene Functionalization Reactions
  • Pd-Catalyzed Alkene Difunctionalization Reactions
  • Pd-Catalyzed Alkene Hydrofunctionalization Reactions

Enantioselective Heck-type Reactions Enantioselective Catalysis and Ligand Design

  • Physical Organic Chemistry in Catalyst Design using Multidimensional Optimization
  • Asymmetric Catalytic Carbonyl Allylation with Cr Complexes

Novel Diarylmethines as Lead Compounds for Breast Cancer Therapy

  • Medicinal Chemistry and Chemical Biology
  • Target Identification
  • Mechanism of Action

Studies Member of the Center for Stereoselective C-H Functionalization (website)

  • Design of new catalysts for C-H functionalization
  • Collaborative research with other team members

topSelected Publications

  • Stokes, B. J.; Opra, S. M.; Sigman, M. S.* “Pd-Catalyzed Allylic C–H Aryl- and Vinylation Reactions of Primary- and Secondary Homoallylic Tosylates,” J. Am. Chem. Soc. 2012, ASAP.
  • Harper, K. C.; Bess, E. N.; Sigman, M. S.* “Multidimensional Steric Parameters in the Analysis of Asymmetric Catalytic Reactions,” Nature Chem. 2012, 4, 366-374. News and Views: Miller, S. J. “Asymmetric catalysis: Correlating sterics in catalysis,” Nature Chem. 2012, 4, 344.
  • Sigman, M. S.*; Werner, E. W. “Imparting Catalyst-Control upon Classical Palladium-Catalyzed Alkenyl C-H Bond Functionalization Reactions” Acc. Chem. Res. 2012, 45, 874-884.
  • Harper, K. C.; Sigman, M. S.* “3-D Correlation of Steric and Electronic Free Energy Relationships Guides Asymmetric Propargylation,” Science 2011, 333, 1875-1878; Perspective: Wiest, O.; Helquist, P. Science 2011, 333, 1831-1832; Highlighted: Chem. & Eng. News 2011, 89 (40), 13.
  • DeLuca, R. J.; Sigman, M. S.* “Anti-Markovnikov Hydroalkylation of Allylic Amine Derivatives via a Palladium-Catalyzed Reductive Cross-Coupling Reaction” J. Am. Chem. Soc. 2011, 133, 11454.
  • Werner, E. W.; Sigman, M. S.* “Operationally Simple and Highly (E)-Styrenyl-Selective Heck Reactions of Electronically Non-Biased Olefins” J. Am. Chem. Soc. 2011, 133, 9692-9695.
  • Michel, B. W.; Steffens, L. D.; Sigman, M. S.* “On the Mechanism of the Palladium-Catalyzed TBHP-Mediated Wacker-Type Oxidation of Alkenes using Quinoline-2-Oxazoline Ligands” J. Am. Chem. Soc. 2011, 133, 8317-8325.
  • Liao, L.; Jana, R.; Urkalan, K. B.; Sigman, M. S.* “A Palladium-Catalyzed Three Component Cross-Coupling of Conjugated Dienes or Terminal Alkenes with Vinyl Triflates and Boronic Acids” J. Am. Chem. Soc. 2011, 133, 5784-5787.
  • Harper, K. C.; Sigman, M. S.* “Predicting and Optimizing Asymmetric Catalyst Performance Using the Principles of Experimental Design and Steric Parameters,” Proc. Nat. Acad. Sci. 2011, 108, 2179-2183.
  • Werner, E. W.; Sigman, M. S.* “A Highly Selective and General Palladium Catalyst for the Oxidative Heck Reaction of Electronically Non-Biased Olefins,” J. Am. Chem. Soc. 2010, 132, 13981-13983.
  • Michel, B. W.; McCombs, J. R.; Winkler, A.; Sigman, M. S.* “Catalyst Contolled Wacker-Type Oxidation of Protected Allylic Amines,” Angew. Chem. Int. Ed. 2010, 49, 7312-7315.
  • Pathak, T. P.; Gligorich, K. M.; Welm, B. E.; Sigman, M. S.* “Synthesis and Preliminary Biological Studies of 3-Substituted Indoles Accessed by a Palladium-Catalyzed Enantioselective Alkene Difunctionalization Reaction” J. Am. Chem. Soc. 2010, 132, 7870-7871.