Chemistry at Illinois University of Illinois at Urbana-Champaign

Scott E. Denmark

Reynold C. Fuson Professor of Chemistry

Scott E. Denmark was born in Lynbrook, NY in 1953. He obtained a S. B. from the Massachusetts Institute of Technology in 1975 and a D.Sc. Tech. from the ETH-Zürich under the direction of Albert Eschenmoser in 1980. That same year he was appointed as assistant professor at the University of Illinois and since 1991 has been the Reynold C. Fuson Professor of Chemistry.

Professor Denmark’s research involves the invention of new synthetic reactions, mechanistic and stereochemical aspects of carbon-carbon bond forming reactions and the design and development of asymmetric catalysts using chemoinformatics.

Professor Denmark has won a number of honors including the Pedler and Robert Robinson Medals (RSC), the Aldrich Award for Creative Work in Synthetic Organic Chemistry, Brown Award for Creative Research in Synthetic Methods, the F. S. Kipping Award in Silicon Chemistry (ACS) and the Prelog Medal.  He is currently the Editor in Chief and President of Organic Reactions.

Research

The research in my group is primarily involved with the invention of new synthetic reactions, on the origin of stereocontrol in fundamental carbon-carbon and carbon-heteroatom bond forming reactions, and in the application of these developments to the synthesis of complex molecular structures. A continuing theme of the work in these laboratories is the relationship between structure, reactivity and stereoselectivity in a variety of organo-element systems, particularly, silicon, phosphorus, tin, sulfur and lithium containing compounds. In recent years this interest has focused on palladium catalyzed cross-coupling reactions with organofunctional silicon compounds, asymmetric catalysis of carbonyl and olefin addition reactions and chiral Lewis base activation of Lewis acids. In addition my research program encompasses the development and application of tandem heterodiene cycloadditions for the synthesis of complex natural (alkaloids) and unnatural (fenestranes) nitrogen containing compounds. In recent years the tandem cycloaddition has been employed as a discovery engine for the investigation of structure/selectivity-reactivity relationships in asymmetric phase transfer catalysis with chiral quaternary ammonium ions.

My group maintains a long-standing interest in catalytic enantioselective reactions with organozinc and other organometallic reagents.

Publications

  1. Development of Chiral Bis-hydrazone Ligands for the Enantioselective Cross-Coupling Reactions of Aryldimethylsilanolates (with W. –T. T.  Chang, K. N. Houk, and P. Liu) J. Org. Chem. 2015, 80, 313-366.
  2. Mechanistic, crystallographic, and computational studies on the catalytic, enantioselective sulfenofunctionalization of alkenes (with E. Hartmann, D. J. P. Kornfilt, and H. Wang) Nature Chemistry, 2014, 6, 1056-1064.
  3. Catalytic, Enantioselective Sulfenylation of Ketone-Derived Enoxysilanes (with S. Rossi, M. P. Webster, and H. Wang) J. Am. Chem. Soc. 2014, 136, 13016-13028.
  4. ExCage (with E. J. Dale, N. A. Vermeulen, A. A. Thomas, J. C. Barnes, M. Juríček, A. K. Blackburn, N. L. Strutt, A. A. Sarjeant, C. L. Stern, and J. F. Stoddart) J. Am. Chem. Soc., 2014, 136, 10669-10682.
  5. Enantioselective Construction of Quaternary Stereogenic Carbon Atoms by the Lewis Base Catalyzed Additions of Silyl Ketene Imines to Aldehydes (with T. W. Wilson and M. T. Burk) Chem. Eur. J. 2014, 20, 9268-9279.
  6. Catalytic, Nucleophilic Allylation of Aldehydes with 2-Substituted Allylic Acetates: Carbon-Carbon Bond Formation Drive by the Water-Gas Shift Reaction (with Z. D. Matesich) J. Org. Chem. 2014, 79, 5970-5986.
  7. Development and Mechanism of an Enantioselective Bromocycloetherification Reaction via Lewis Base/Chirol Brønsted Acid Cooperative Catalysis (with M. T. Burk) Chirality, 2014, 26, 344-355.
  8. Lewis Base Catalyzed, Enantioselective, Intramolecular Sulfenoamination of Olefins (with H. M. Chi) J. Am. Chem. Soc. 2014, 136, 8915-8918.
  9. Catalytic, Enantioselective, Intramolecular Carbosulfenylation of Olefins.  Mechanistic Aspects: A Remarkable Case of Negative Catalysis (with H. M. Chi) J. Am. Chem. Soc. 2014, 136, 3655-3663.
  10. Catalytic Conjugate Addition of Acyl Anion Equivalents Promoted by Fluorodesilylation (with L. R. Cullen) Org. Lett. 2014, 16, 70-73.
  11. Catalytic, Enantioselective, Intramolecular Carbosulfenylation of Olefins.  Preparative and Stereochemical Aspects (with A. Jaunet) J. Org. Chem. 2014, 79, 140-171.
  12. Asymmetric Construction of Quaternary Stereogenic Centers via Auxiliary-Based SN2’ Reactions: A Case of 1,7-Relative Stereogenesis (with L. K. Marble) Heterocycles 2014, 88, 559-590.
  13. Iron-Catalyzed Cross-Coupling of Unactivated Secondary Aryl Thio Ethers and Sulfones with Aryl Grignard Reagents (with A. J. Cresswell) J. Org. Chem. 2013, 78, 12593-12628.
  14. Lewis Base Activation of Lewis Acids: Group 13. In Situ Generation and Reaction of Borenium Ions (with Y. Ueki) Organometallics 2013, 32, 6631-6634.
  15. Lewis Base Catalysis of the Mukaiyama Directed Aldol Reaction: 40 Years of Inspiration and Advances (with G. L. Beutner) Angew. Chem. Int. Ed. 2013, 52, 9086-9096.
  16. Catalytic, Enantioselective, Intramolecular Carbosulfenylation of Olefins (with A. Jaunet) J. Am. Chem. Soc. 2013, 135, 6419-6422.
  17. A Theoretical Investigation on the Mechanism and Stereochemical Course of the Addition of (E)-2-Butenyltrimethylsilane to Acetaldehyde by Electrophilic and Nucleophilic Activation (with L. M. Wolf) J. Am. Chem. Soc. 2013, 135, 4743-4756.
  18. Carbanion-Accelerated Claisen Rearrangements: Asymmetric Induction with Chiral Phosphorus-Stabilized Anions (with J. E. Marlin and G. Rajendra) J. Org. Chem. 2013, 78, 66-82.

Additional Denmark Group Publications

Awards

  • Eli Lilly Research Award, 1983
  • Beckman Endowment Research Award, 1983
  • University of Illinois Center for Advanced Study, Beckman Fellow, Spring 1985
  • A. P. Sloan Foundation Fellow, 1985-1987
  • NSF Presidential Young Investigator Award, 1985-1990
  • Procter and Gamble University Exploratory Research Program Award, 1986-1989
  • University Scholar, University of Illinois, 1986-1989
  • School of Chemical Sciences Teaching Award, University of Illinois, 1986
  • Stuart Pharmaceuticals Award in Chemistry, ICI Americas, 1987
  • A. C. Cope Scholar Award, American Chemical Society, 1989
  • Alexander Von Humboldt Senior Scientist Award, 1990
  • Fellow, American Association for the Advancement of Science, 1990
  • Reynold C. Fuson Professor of Chemistry, 1991-present
  • Pedler Medal (Royal Society of Chemistry), 2002-2003
  • ACS Award for Creative Work in Synthetic Organic Chemistry, 2003
  • Yamada-Koga Prize (Japan Research Foundation for Optically Active Compounds), 2006
  • Fellow, Royal Society of Chemistry, 2006
  • Prelog Medal (ETH-Zürich, Switzerland), 2007
  • Robert Robinson Medal and Lectureship (Royal Society of Chemistry) 2008
  • Herbert C. Brown Award for Creative Research in Synthetic Methods (ACS), 2009
  • Fellow, American Chemical Society, 2009 (inaugural year)
  • ISHC Senior Award in Heterocyclic Chemistry, 2011
  • Frederic Stanley Kipping Award in Silicon Chemistry (ACS), 2014
  • Harry and Carol Mosher Award of the Santa Clara Section of the ACS, 2014

Highlights

Professinal Activities

  1. NSF Workshop on Synthetic Organic and Natural Products Chemistry, Co-Chairman (1987-1989)
  2. Executive Committee, Organic Division, American Chemical Society (1989-1992)
  3. Cope Scholar Award Canvassing Committee (1992-1994)
  4. International Advisory Board, Perkin Transactions 1 (1992-1994)
  5. AAAS Chemistry Section, Electorate Nominating Committee (1998-2001)
  6. Gordon Research Conference on Heterocyclic Compounds, Vice Chair, 2000; Chair, 2001.

Professional Societies

  • American Chemical Society
  • New Swiss Chemical Society
  • Royal Society of Chemistry
  • American Association for the Advancement of Science

Editorial Activities

  1. Editorial Board, Organic Reactions (1994-2003)
  2. Editorial Board, Encyclopedia of Reagents for Organic Synthesis
  3. Editorial Advisory Board, Journal of Organic Chemistry (1995- 2000)
  4. Editorial Advisory Board, Accounts of Chemical Research (1997- 2000)
  5. Guest Editor Thematic Issue "Catalytic Asymmetric Synthesis" in Accounts Chem. Res. 2000, 38(6).
  6. Editorial Advisory Board, Progress in Heterocyclic Chemistry (1997-2001)
  7. Editor, Topics in Stereochemistry (1995-2007)
  8. Associate Editor, Organic Letters (1998-2004)
  9. Editorial Board, Organic Syntheses, Inc. (2000-2008)
  10. Board of Directors, Organic Reactions (2004-present)
  11. Editorial Advisory Board, Organic Letters (2005-present)
  12. President and Editor-in-Chief, Organic Reactions (2008-present)
  13. Board of Consulting Editors, Tetrahedron (2008-present)
  14. Editorial Advisory Board, Chemical Communications (2007- present)
  15. Editorial Advisory Board Chemical Reviews (2010-present)
  16. Editor, Organic Synthesis, Vol. 85
  17. Editorial Advisory Board, Journal of Organic Chemistry (2011-present)

Consultantships

  • Pharmacia (formerly Upjohn), Kalamazoo, Michigan, 1983-2003
  • Pfizer, Ann Arbor, Michigan, 2003-2006
  • Dow Chemical Company, Midland Michigan, 1986-1989
  • LIGAND Pharmaceuticals, La Jolla, California, 1993-1998
  • Boehringer-Ingelheim Pharmaceuticals, Ridgefield, CT, 2000-present
  • Johnson and Johnson Pharmaceutical Research Institute, San Diego, CA, 2001-present
  • Merck Research Laboratories, Rahway, NJ, 2004-2009
  • Milliken Chemical Company, Spartanburg, SC 2006-present
  • Genentech, San Francisco, CA, 2008-present
  • GlaxoSmithKline, Raleigh-Durham, NC, 2009-2010
  • PTC Therapeutics, South Plainfield, NJ, 2008-present
  • Dart Neurosciences, San Diego, CA, 2011-present
  • Coferon, New York, NY, 2011-present

Scientific Advisory Boards

  • LIGAND Pharmaceuticals, La Jolla, California, 1996-1998
  • The Pharmacia and Upjohn Company, Kalamazoo, Michigan, 1998-1999

Patents

Photo of Scott E. Denmark