NIU Department of
Chemistry & Biochemistry
Where the study of matter...matters!
Associate Professor
Office: Faraday Hall 335
Phone: (815) 753-1959
dklumpp@niu.edu
Postdoctoral Fellow, University of Southern California, 1993-1996
Ph.D., Iowa State University, 1993
B.S., University of Oklahoma, 1987
Synthetic and mechanistic organic chemistry; reactive chemical intermediates; chemistry of reactive electrophilic systems; asymmetric synthesis, polymer functionalization, metal chelating polymers, pyrolysis; fuel chemistry; agrochemicals.
Superelectrophiles and Their Chemistry. Olah, G. A.; Klumpp, D. A. (2007) John Wiley & Sons, New York.
Superacid promoted reactions of N-acyliminium salts and evidence for the involvement of superelectrophiles. Zhang, Y.; DeSchepper, D. J.; Gilbert, T. M.; Klumpp, D. A. (2007) Chem. Comm., in press.
Aza-Nazarov reaction and the role of superelectrophiles. Klumpp, D. A.; Zhang, Y.; O’Connor, M. J.; Esteves, P. M.; de Almeida, L. S. (2007) Organic Letters, 9: 3085-3088.
Superacid-catalyzed reactions of pyridinecarboxaldehydes. Klumpp, D. A.; Zhang, Y.; Kindelin, P. J.; Lau, S. (2006) Tetrahedron, 62: 5915.
Superacid-catalyzed reactions of N-acylimines: a convenient route to tetrahydroquinoline and the role of superelectrophiles. Zhang, Y.; Kindelin, P. J.; DeSchepper, D.; Zheng, C.; Klumpp, D. A. (2006) Synthesis, 1775.
Charge migration in dicationic electrophiles and its application to the synthesis of aza-polycyclic aromatic compounds. Li, A.; Kindelin, P. J.; Klumpp, D. A. (2006) Organic Letters, 8: 1233.
Superacid-catalyzed reactions of olefinic pyrazines: An example of anti-Markovnikov addition involving superelectrophiles. Zhang, Y.; Briski, J.; Zhang, Y.; Rendy, R.; Klumpp, D. A. (2005) Organic Letters, 7: 2505.
My research is in the area of synthetic and mechanistic organic chemistry. Much of our work involves the study of reactive chemical intermediates. We seek new methods of generating reactive intermediates and new chemical systems that are prone to forming reactive species in solution. In generating these intermediates, we can often take advantage of their reactivities in synthetic reactions.
We have a longstanding interest in the chemistry of reactive electrophilic systems. Using strong and superacidic media, dicationic electrophilic intermediates can be readily generated. The dicationic intermediates can be much more reactive than comparable, monocationic electrophiles. We have taken advantage of this reactivity in synthetic reactions (for example, in the preparations of phenytoin, an important anti-epileptic drug, eq. 1, and fenpiprane, an anti-spasmodic drug, eq. 2).
(1)
(2)
Our work has also demonstrated that common cationic functional groups can significantly activate adjacent electrophilic sites. For example, the phosphonium group is known to stabilize adjacent anions in the familiar chemistry of ylids (Wittig reactions). We found that phosphonium groups enhance the reactivities of (i.e., destabilize) adjacent carboxonium and carbocation sites (eq. 3). In some cases, we have also been able to directly observe the reactive, dicationic electrophiles through the use of spectroscopic techniques such as low-temperature NMR. Through the study of these reactive electrophiles, we strive to gain further understanding of chemical reactivity and develop new methods of organic synthesis.
(3)
In addition to the chemistry of electrophilic systems, we have also been working in the areas of asymmetric synthesis, polymer functionalization, the design of metal chelating polymers, pyrolysis of organic materials, fuel chemistry, and agrochemicals.