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

“Predictive Model for Oxidative C–H Functionalization Reactivity with 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone,” Morales-Rivera, C. A.; Floreancig, P. E.; Liu, P. , J. Am. Chem. Soc., Vol. 139, 2017, Pages 17935-17944
“Re2O7-Mediated Dehydrative Cyclization Reactions: Application to the Total Synthesis of Herboxidiene and an Analog,” Rohrs, T. M.; Qin, Q.; Floreancig, P. E. , Angew. Chem., Int. Ed., Vol. 56, 2017, Pages 10900-10904
“Alcohol, Aldehyde, and Ketone Liberation and Intracellular Cargo Release through Peroxide-Mediated α-Boryl Ether Fragmentation,” Hanna, R. D.; Naro, Y.; Deiters, A.; Floreancig, P. E. , J. Am. Chem. Soc., Vol. 138, 2016, Pages 13353-13360
“Convergent One-Pot Oxidative [n+1] Approaches to Spiroacetal Synthesis,” Peh, G. R.; Floreancig, P. E. , Org. Lett., Vol. 17, 2015, Pages 3750-3753
“Polyethers in From Biosynthesis to Total Synthesis,” Xie, Y.; Floreancig, P. E., Zografos, A. L., Ed. Wiley ,
“Structure Inspires a New Method that Delivers the Synthesis of Natural Products and Analogs in the Pederin Family,” Floreancig, P. E. , Strategies and Tactics in Organic Synthesis Harmata, M., Ed. Elsevier, 2015, Pages 183-205
“Allylic Alcohol Transposition-Based Heterocycle Synthesis Using Traceless Trapping Groups,” Xie, Y.; Floreancig, P. E. , Angew. Chem., Int. Ed., Vol. 53, 2014, Pages 4926-4929
“Stereocontrolled Cyanohydrin Ether Synthesis through Chiral Bronsted Acid-Mediated Vinyl Ether Hydrocyanation,” Lu, C.; Su, X.; Floreancig, P. E. , J. Org. Chem. , Vol. 78, 2013, Pages 9366-9376
“Bimolecular Coupling Reactions through Oxidatively Generated Aromatic Cations: Scope and Stereocontrol,” Cui, Y.; Villafane, L. A.; Clausen, D. J.; Floreancig, P. E. , Tetrahedron , Vol. 69, 2013, Pages 7618-7626
“Prins-Type Cyclization Reactions in Natural Product Synthesis,” Han, X.; Peh, G. R.; Floreancig, P. E. , Eur. J. Org. Chem., 2013, Pages 1193-1208
“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
“Isolation, Biological Activity, and Medicinal Chemistry of the Pederin/Mycalamide Family of Natural Products,” Mosey, R. A.; Floreancig, P. E. , Nat. Prod. Rep., Vol. 29, 2012, Pages 980-995
“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