Directory: Faculty

Matthew S. Sigman

ORGANIC SYNTHESIS & ASYMMETRIC CATALYSIS

Associate Professor

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

Publications

Activities & Awards

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.

Research Interests

The development of versatile synthetic methods has enhanced the ability to rapidly construct biologically relevant molecules and new organic materials. The goal of the Sigman Group is discovering and developing new practical catalytic reactions with broad substrate scope, excellent chemoselectivity, and high stereoselectivity. We believe the best strategy for developing new classes of catalysts 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. As we gain a deeper fundamental understanding into the nature of catalysis, our long-term goal of de novo design of catalysts applicable to various useful reactions may be realized.

catalytic reactions

Practical Oxidations in Organic Synthesis. The goal of our efforts is to advance the field of oxidation catalysis through the discovery of novel catalytic processes which utilize environmentally benign terminal oxidants such as simple peroxides and molecular oxygen. While initially we were focused on understanding and designing catalysts for Pd-catalyzed aerobic alcohol oxidations, we have recently been investigating novel olefin functionalization reactions. For example, we have recently disclosed two unprecedented dioxygen coupled transformations: a dialkoxylation and hydroalkoxylation of olefins (see above). Initial mechanistic investigation into the hydroalkoxylation process has revealed that the hydrogen incorporated into the product is derived from an alcohol oxidation. Current and future efforts are focused on extending and applying these exciting findings to new reaction development.

Heterocycles in Synthesis and Catalysis. The development of new chiral ligands has played a central role in the discovery of asymmetric catalysts. However, many of the most common ligands, often termed “privileged,” suffer from difficulties in making simple systematic changes to the structure to enhance catalysis. In contrast, a modular synthetic approach allows access to tunable ligand sets. A tunable ligand structure not only leads to enhanced selectivity and activity through optimization but allows for the elucidation of structure-reactivity relationships in order to gain insight into the reaction mechanism.

Heterocycles in Synthesis and Catalysis

We have developed a modular ligand program based on an oxazoline amine core (highlighted in blue above). Using this core structure we have identified two novel asymmetric catalysts for distinct carbon-carbon bond forming catalytic reactions: (a) a Nozaki-Hiyama Kishi allylation reaction and (b) a hydrogen bond promoted Hetero-Diels-Alder reaction. We are currently exploring the fundamental aspects of these transformations in terms of why certain ligands lead to high enantiomeric excess as well as exploring new reactions with related catalysts.

Selected Publications

Miller, J. J.; Sigman, M. S. “Using a Modular Ligand to Systematically Probe the Effect of Sterics in an Enantioselective Reaction: Observation of Linear Free Energy Relationships,” Angew. Chem. Int. Ed. 2007, in press.
Gligorich, K. M.; Cummings, S. A.; Sigman, M. S. “Catalytic Reductive Coupling of Alkenes and Organometallic Reagents under Aerobic Conditions,” J. Am. Chem. Soc. 2007, 129, in press.
Podhajsky, S. M.; Sigman, M. S. “Coupling a Pd-Catalyzed Alcohol Oxidation to Olefin Functionalization: Hydrohalogenation/Hydroalkoxylation of Styrenes,” Organometallics 2007, 26, 5680-5686.
Jensen, K. H.; Sigman, M. S. “Systematically Probing the Effect of Catalyst Acidity in a Hydrogen Bond Catalyzed Enantioselective Reaction,” Angew. Chem. Int. Ed. 2007, 46, 4748-4750; Science & Technology Concentrate in Chem & Eng. News 2007, 85 (21), 31; Editors’ Choice in Science 2007, 316, 1257.
Zhang, Y.; Sigman, M. S. “Palladium(II)-Catalyzed Enantioselective Aerobic Dialkoxylation of 2-Propenyl Phenols: A Pronounced Effect of Copper Additives on Enantioselectivity,” J. Am. Chem. Soc. 2007, 129, 3076-3077.
Miller, J. J.; Sigman, M. S. “Design and Synthesis of Modular Oxazoline Ligands for the Enantioselective Chromium-Catalyzed Addition of Allyl Bromide to Ketones,” J. Am. Chem. Soc. 2007, 129, 2752-2753.
Cornell, C. N.; Sigman, M. S. “Recent Progress in Wacker Oxidations: Moving Toward Molecular Oxygen as the Sole Oxidant,” Inorg. Chem. 2007, 46, 1903-1909.
K. M. Gligorich, M. J. Schultz, M. S. Sigman “Palladium(II)-Catalyzed Aerobic Hydroalkoxylation of Styrenes Containing a Phenol,” J. Am. Chem. Soc. 2006, 128, 2794-2795.
M. S. Sigman, D. R. Jensen “Ligand-Modulated Palladium-Catalyzed Aerobic Alcohol Oxidations” Acc. Chem. Res. 2006, 39, 221-229.
M. J. Schultz, M. S. Sigman “Palladium(II)-Catalyzed Aerobic Dialkoxylation of Styrenes: A Profound Influence of an ortho-Phenol,” J. Am. Chem. Soc. 2006, 128, 1460-1461.
A. M. Balija, K. J. Stowers, M. J. Schultz, M. S. Sigman “Pd(II)-Catalyzed Conversion of Styrene Derivatives to Acetals: Impact of (-)-Sparteine on Regioselectivity,” Org. Lett. 2006, 8, 1121-1124.
S. Rajaram, M. S. Sigman “Design of Hydrogen Bond Catalysts Based on a Modular Oxazoline Template: Application to an Enantioselective Hetero Diels-Alder Reaction,” Org. Lett. 2005, 7, 5473-5475;Editors’ Choice in Science 2005, 310, 1247.
J.-Y. Lee, J. J. Miller, S. S. Hamilton M. S. Sigman “Stereochemical Diversity in Chiral Ligand Design: Discovery and Optimization of Catalysts for the Enantioselective Addition of Allylic Halides to Aldehydes,” Org. Lett. 2005, 7, 1837-1839.
C. N. Cornell, M. S. Sigman “Discovery of and Mechanistic Insight into a Ligand-Modulated Palladium Catalyzed Wacker Oxidation of Styrenes using TBHP,” J. Am. Chem. Soc. 2005, 127, 2796-2797.

M. J. Schultz, S. S. Hamilton, D. R. Jensen, M. S. Sigman “Development and Comparison of Substrate Scope of Pd-Catalysts for the Aerobic Oxidation of Alcohols” J. Org. Chem. 2005, 70, 3343-3352.