Department of Chemistry at Illinois State University

Chemistry People


Nagorski

Richard W Nagorski

Professor, Organic Chemistry
Associate Chair of Graduate Programs

Office Address: 219 Science Laboratory Building
Office Phone: (309)438-8978
Office Hours: M 10-10:50 a.m., W 12-1 p.m. or by appointment
Email: Contact Richard Nagorski (rnagor)
Website: Visit Richard Nagorski’s Website
Teaching Schedule:
Course NumberSectionCourse NameTimeRoom NumberCourse Links
CHE232.01Organic Chemistry II M W F 11:00 - 11:50MLT 0210
CHE233.02Organic Chemistry Laboratory II T R 12:00 - 14:50SLB 0105
CHE233.02Organic Chemistry Laboratory II T R 12:00 - 14:50SLB 0105
CHE290.014Research in Chemistry   
CHE299.014Independent Honor Study in Chemistry   
CHE490.014Research in Chemistry   
Teaching Interests:
Research Interests:

Areas of Current Research Interest

The area of general interest within our group is the mechanisms and rate constants of reaction of biologically important molecules in water. In general, we prefer to observe the reaction of simple molecular analogs of the biological molecules of interest and extend our observations to the more complex biological molecules as our understanding of the system increases.

There are two areas of current interest within the group. The first is the investigation of the stability constants and specifically, the mechanism of breakdown of carbinolamides. The general structure of carbinolamides is as shown in Scheme 1, and allows for great diversity of groups given the three possible positions of substitution. We are interested in these compounds because it has been shown that carbinolamides are intermediates in the enzyme mediated synthesis of a-amidated peptides. However, very little systematic work on the reaction of carbinolamides has been completed and even less is known about methods to catalyze the breakdown of these compounds.

We propose the study of the reaction of various carbinolamides under aqueous conditions and the factors that catalyze their breakdown.

The second area of current interest is the electrophilicity of amides, that is, how susceptible are amides to nucleophilic attack by a carbanion. Shown in Scheme 2 is the general reaction in which we are interested. The reaction proceeds by the formation of an enolate which can then nucleophilically attack the amide to form 2. Compound 2 will then undergo breakdown to form products. There are many interesting aspects to this reaction, the first of which is the reaction itself. We are familiar with similar reactions of this type (eg. Aldol, Claisen, Dieckmann) but this particular reaction has itself received little or no attention. Secondly, by investigating this reaction we will generate data that will allow us to make conclusions about the electrophilicity of amides that may eventually allow a better understanding of resonance.

We propose the study of the mixed-Claisen condensation reaction above to determine the nature of this reaction and gain insight into the electrophilicity of amides. In addition, by changing the R groups on nitrogen we may be able to measure changes in the electrophilicity of the amide.

Skills and Techniques of Importance:

Students (undergraduate and graduate) who work in my labs will receive a variety of experiences:

  • synthesis and purification of organic compounds

  • learn the proper techniques for the determination and analysis of kinetic data and then put these techniques to use

  • learn the operation of analytical instrumentation for the purposes of isolation and identification of reaction products

  • spectral identification of organic compounds and become familiar with methods of obtaining said spectra

Education:
Selected Publications:
S. M. Cope, D. Tailor, R. W. Nagorski, "Determination of the pKa of Cyclobutanone: Brønsted Correlation of the General Base-Catalyzed Enolization in Aqueous Solution and the Effect of Ring Strain," Journal of Organic Chemistry, 2011, 76 (2), 380-390. doi:10.1021/jo101369w

M. F. Sansone, T. Koyanagi, D. E. Przybyla, R. W. Nagorski, "Solvent-Free Synthesis of Monoacylaminals from the Reaction of Amides and Aminals as Precursors in Carbinolamide Synthesis," Tetrahedron Letters, 2010, 51 (46), 6031-6033. doi:10.1016/j.tetlet.2010.09.043

J. L. Murphy, W. J. Tenn III, J. J. Labuda, R. W. Nagorski, "Rapid Amidic Hydrolysis: A Competitive Reaction Pathway Under Basic Conditions for N-(Hydroxymethyl)benzamide Derivatives Bearing Electron-Donating Groups," Tetrahedron Letters, 2009, 50 (52), 7358-7361. doi:10.1016/j.tetlet.2009.10.069

R. V. Ankem, J. L. Murphy, R. W. Nagorski, "Rate of Formation of N-(Hydroxymethyl)benzamide Derivatives in Water as a Function of pH and Their Equilibrium Constants," Tetrahedron Letters, 2008, 49 (46), 6547-6549. doi:10.1016/j.tetlet.2008.09.009

W. J. Tenn III, J. L. Murphy, J. K. Bim-Merle, J. A. Brown, A. J. Junia, M. A. Price, R. W. Nagorski, "Amidates as Leaving Groups: Structure/Reactivity Correlation of the Hydroxide-Dependent E1cB-like Breakdown of Carbinolamides in Aqueous Solution," The Journal of Organic Chemistry, 2007, 72 (16), 6075-6083. doi:10.1021/jo070603u

A. G. Mennenga, A. L. Johnson, R. W. Nagorski, "General-Buffer Catalysis of the Reaction of N-(Hydroxymethyl)benzamide: A New Pathway for the Aqueous Reaction of Carbinolamides," Tetrahedron Letters, 2005, 46 (17), 3079-3083. doi:http://dx.doi.org/10.1016/j.tetlet.2005.03.011

R. J. Cantlin, J. Drake, R. W. Nagorski, "Ring Strain and Its Effect on the Rate of the General-Base Catalyzed Enolization of Cyclobutanone," Organic Letters, 2002, 4 (14), 2433-2436. doi:10.1021/ol0261938