Department of Chemistry

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Paul Floreancig

Professor, and Director of Graduate Studies

Contact

1403 CHVRN
Chevron Science Center
219 Parkman Avenue

Pittsburgh, PA 15260
412-624-8727

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Research Overview

Organic Synthesis

Our research is directed toward developing fundamentally new transformations and highlighting their utility for complex molecule synthesis. Much of our work in reaction design has been devoted to utilizing oxidation processes to form electrophiles. These processes exploit the high but predictable cleavage patterns of radical cations and utilize unconventional leaving groups such as benzyl radicals of hydrogen atoms as leaving groups in cation-forming reactions. These studies draw heavily upon basic principles of physical organic chemistry to provide highly chemoselective and efficient cyclization reactions that proceed under mild conditions.

We are also devising methods that utilize the capacity of nitriles to act as precursors to highly functionalized amides. This multicomponent process proceeds through nitrile hydrozirconation, acylation of the resulting metalloimine, and nucleophilic addition to the intermediate acylimine. The process can be applied to the formation of carbon–carbon or carbon–heteroatom bonds, making it quite useful for applications to combinatorial and diversity-oriented synthesis. The generally inert nature of nitriles also creates unique strategic opportunities for target-oriented synthesis that minimize protecting group manipulations.

The inspiration for our efforts in natural product synthesis range from preparing inaccessible materials with interesting biological activities to demonstrating the capacity of our methods to function in a complex setting. Examples of complex structures that we have recently prepared are shown below.

Awards

  • Research Innovation Award, Research Corporation, 2001
  • NIH Postdoctoral Fellowship, 1997-1999; Roche Award for Excellence in Organic Chemistry, 1995

Publications

“Cyclopropane Compatibility with Oxidative Carbocation Formation: Total Synthesis of Clavosolide A,” Peh, G. R.; Floreancig, P. E., Org. Lett., Vol. 14, 2012, Pages 5614-5617
“Aromatic Cations from Oxidative Carbon–Hydrogen Bond Cleavage in Bimolecular Carbon–Carbon Bond Forming Reactions,” Clausen, D. J.; Floreancig, P. E., J. Org. Chem., Vol. 77, 2012, Pages 6574-6582
“Versatile Approach to Alpha-Alkoxy Carbamate Synthesis and Stimulus-Responsive Alcohol Release,” Mosey, R. A.; Floreancig, P. E., Org. Biomol. Chem., Vol. 10, 2012, Pages 7980-7985
“Synthesis of Sulfur-Containing Heterocycles through Oxidative Carbon–Hydrogen Bond Functionalization,” Cui, Y.; Floreancig, P. E., Org. Lett., Vol. 14, 2012, Pages 1720-1723
“Synthesis and biological evaluation of neopeltolide and analogs,” Cui, Y., Balachandran, R., Day, B.W., Floreancig, P.E., J. Org. Chem., Vol. 77, 2012, Pages 2225-2235
“Stereoselective Piperidine Synthesis through Oxidative Carbon–Hydrogen Bond Functionalization of Enamides,” Brizgys, G. J.; Jung, H. H.; Floreancig, P. E., Chem. Sci., Vol. 3, 2012, Pages 438-442
“Total Synthesis of Pederin, Psymberin, and Highly Potent Analogs,” Wan, S.; Wu, F.; Rech, J. C.; Green, M. E.; Balachandran, R.; Horne, W. S.; Day, B. W.; Floreancig, P. E., J. Am. Chem. Soc., Vol. 133, 2011, Pages 16668-16679
“Total Synthesis of the Protein Phosphatase 2A Inhibitor Lactodehydrothyrsiferol,” Clausen, D. J.; Wan, S.; Floreancig, P. E., Angew. Chem., Int. Ed., Vol. 50, 2011, Pages 5178-5181
“Total Synthesis of Pederin and Analogs,” Wu, F.; Green, M. E.; Floreancig, P. E., Angew. Chem., Int. Ed., Vol. 50, 2011, Pages 1131-1134
“Stereoselective Synthesis of Spirooxindole Amides through Nitrile Hydrozirconation,” Lu CL, Xiao Q, Floreancig PE, Organic Letters, Vol. 12, 2010, Pages 5112-5115
“Stereoselective Synthesis of Tertiary Ethers through Geometric Control of Highly Substituted Oxocarbenium Ions,” Liu L, Floreancig PE, Angewandte Chemie-International Edition, Vol. 49, 2010, Pages 5894-5897
“Synthesis of Structurally and Stereochemically Diverse Tetrahydropyrans through Oxidative Carbon–Hydrogen Bond Activation,” Liu, L.; Floreancig, P. E., Angew. Chem., Int. Ed., Vol. 49, 2010, Pages 3069-3072, DOI: 10.1002/anie.201000033
“Stereoselective heterocycle synthesis through oxidative carbon-hydrogen bond activation,” Liu L, Floreancig PE, Current Opinion in Drug Discovery & Development, Vol. 13, 2010, Pages 733-747
“Rapid Catalyst Screening by a Continuous-Flow Microreactor Interfaced with Ultra High Pressure Liquid Chromatography,” Hui F.; Qing, X.; Wu, F.; Floreancig, P. E.; Weber, S. G., J. Org. Chem., Vol. 75, 2010, Pages 5619-5626
“Total synthesis of neopeltolide and analogs,” Cui YB, Tu WY, Floreancig PE, Tetrahedron, Vol. 66, 2010, Pages 4867-4873
“Structurally and Stereochemically Diverse Tetrahydropyran Synthesis through Oxidative CH Bond Activation,” Liu L, Floreancig PE, Angewandte Chemie International Edition, Vol. 49, 2010, Pages 3069-3072
“Cyclization Reactions through DDQ-Mediated Vinyl Oxazolidinone Oxidation,” Liu L, Floreancig PE, ORGANIC LETTERS, Vol. 11, 2009, Pages 3152-3155
“Oxidative Carbocation Formation in Macrocycles: Synthesis of the Neopeltolide Macrocycle,” Tu WY, Floreancig PE, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, Vol. 48, 2009, Pages 4567-4571
“Total synthesis of theopederin D,” Green ME, Rech JC, Floreancig PE, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, Vol. 47, 2008, Pages 7317-7320
“Diastereoselective tetrahydropyrone synthesis through transition-metal-free oxidative carbon-hydrogen bond activation,” Tu WY, Liu L, Floreancig PE, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, Vol. 47, 2008, Pages 4184-4187
“Multicomponent approach to the synthesis of oxidized amides through nitrile hydrozirconation,” Wan S, Green ME, Park JH, Floreancig PE, ORGANIC LETTERS, Vol. 9, 2007, Pages 5385-5388
“Oxidative cleavage in the construction of complex molecules: Synthesis of the leucascandrolide A macrolactone,” Jung HH, Seiders JR, Floreancig PE, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, Vol. 46, 2007, Pages 8464-8467
“An experimental and computational approach to defining structure/reactivity relationships for intramolecular addition reactions to bicyclic epoxonium ions,” Wan S, Gunaydin H, Houk KN, Floreancig PE, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Vol. 129, 2007, Pages 7915-7923