University of Pittsburgh

Paul Floreancig

Contact Info:

Department of Chemistry
Chevron Science Center
219 Parkman Avenue
Pittsburgh, PA 15260

Office: 1403 CHVRN
Phone: 412-624-8727

Professor

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

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, http://pubs.acs.org/doi/pdfplus/10.1021/jo2023685
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, http://pubs.acs.org/doi/pdf/10.1021/ja207331m
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, http://onlinelibrary.wiley.com/doi/10.1002/anie.201007757/pdf
Total Synthesis of Pederin and Analogs,” Wu, F.; Green, M. E.; Floreancig, P. E. , Angew. Chem., Int. Ed., Vol. 50, 2011, Pages 1131-1134, http://onlinelibrary.wiley.com/doi/10.1002/anie.201006438/pdf
Stereoselective Synthesis of Spirooxindole Amides through Nitrile Hydrozirconation,” Lu CL, Xiao Q, Floreancig PE , Organic Letters, Vol. 12, 2010, Pages 5112-5115, http://pubs.acs.org/doi/pdfplus/10.1021/ol102246d
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, http://www.biomedcentral.com/content/pdf/cd-1144494.pdf
Total synthesis of neopeltolide and analogs,” Cui YB, Tu WY, Floreancig PE , Tetrahedron, Vol. 66, 2010, Pages 4867-4873, http://www.sciencedirect.com/science?_ob=MImg&_imagekey=B6THR-4YPT1KP-3-10&_cdi=...
Cyclization Reactions through DDQ-Mediated Vinyl Oxazolidinone Oxidation,” Liu L, Floreancig PE, ORGANIC LETTERS, Vol. 11, 2009, Pages 3152-3155, http://pubs.acs.org/doi/pdf/10.1021/ol901188q
Total synthesis of theopederin D,” Green ME, Rech JC, Floreancig PE, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, Vol. 47, 2008, Pages 7317-7320, http://www3.interscience.wiley.com/cgi-bin/fulltext/121371657/PDFSTART
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, http://pubs.acs.org/doi/pdfplus/10.1021/ol702184n