Albert J. Fry, PhD
Professor of Organic Chemistry
and E. B. Nye Professor of Chemistry

We have two major projects underway. In one, we are studying the electrochemical oxidation of conjugated alkenes, 1,1-and 1,2-diphenylethylenes (stilbenes). The course of reaction seems to depend on the nature of the substituents on the aromatic rings. Stilbenes in which the benzene rings bear anywhere from two to four strong electron-withdrawing groups undergo conversion to aldehydes in high yield in acentonitrile containing a small amount of water. We have termed this an electrochemical equivalent of ozonolysis. On the other hand, stilbenes bearing electron-supplying or weakly electron-withdrawing groups are converted into benzophenones under the same conditions. We suspect that the two types of reaction both involve a b-hydroxy carbocation. This could either (a) react with water to afford a vic-diol, which would then be oxidatively cleaved to two aldehyde molecules, or (b) undergo a pinacol-type rearrangement to afford a diarylacetaldehyde, which could be oxidatetively converted to the benzophenone via its enol. Mechanistic studies are being carried to establish the origin of the substituent effect. In related work, the anodic oxidation of cycloocatetraene is being studied in hydrolytic solvents. Here too, the same dichotomy between either reaction of an intermediate b-oxy carbocation or carbon skeletal rearrangement seems to be operative. We are studying the dependence of the products upon the nature of the solvent to both better understand the mechanism of the reactions and search for synthetic applications.

A second project involves application of quantum chemical computational techniques to electrochemical problems that cannot be solved by experimental means. Much of the work has involved dissecting the relative contributions of solvation and ion-pairing to the electrochemical behavior of polycyclic aromatic hydrocarbons and thus explaining anomalies in such behaviors. Other work has involved: (a) elucidation of the mechanism of anodic oxidation of cycloocatetraene in hydroxylic solvents; (b) development of highly accurate and methods for treatment of substituent effects upon the electrochemical reduction and oxidation of organic substrates; and (c) the discovery by computational means that many organic cations are surrounded by a strongly held sheath of solvent molecules and that this sheath often has dramatic effect upon the electrochemical behavior of such cations.

    
  Selected Publications

• "Tetraalkylammonium Ions Are Surrounded By An Inner Solvation Shell in Strong Electron Pair Donor Solvents", Fry, A. J.; Electrochemistry Communications, 11, 309, (2009)
   

• "Substituent Effects on the Redox Properties and Structure of Substituted Triphenylamines. An Experimental and Computational Study", Wu, X.; Davis, A.; Lambert, P. C.; Steffen, L. K.; Toy, O.; Fry, A .J.; Tetrahedron, 65, 2408, (2009).
   

• "Computational Examination of Substituent Effects on the Interconversion of 1.3.5- Cyclooctatriene and Bicyclo[4.2.0]-2.4-octadiene.", Fry, A. J.; Tetrahedron, 64, 2101 (2008) 
   

•  "Electrocatalytic Cleavage of Electronegatively Substituted Stilbene Employing a New High Potential Electrocatalystst: An Electrochemical Equivalent of Ozonolysis.", Wu, X., et al. and Fry, A. J., Organic Letters, 9 5633 (2007).
   
• "Computational Study of the Interaction Between the 1,4-Dinitrobenzene Dianion and Substituted Imidazolium Ions", Minami, Y; Fry, A. J.; Proceedings of the international Conference on Computational Methods in Science and Engineering, Corfu Greece, Minami, Y.; Fry A. J.; 2A, 481-484, (2007).
   
• "Experimental/Computational Study of the Electrochemical Oxidation of Cyclooctatetraene in Protic Media. Solvent Effects", Connors, G.; Fry, A. J.; Wu, X.; Organic Letters, 9, 1671. (2007).
   
• "Effects of Strong Ion-Pairing on the Electrochemical Reduction of Cyclooctatetraene in Tetrahydrofuran in the Presence of Lithium Ion. Peak Coalescence Does not  Imply Potential Inversion", Fry, A. J.; Electroanalysis, 18, 379, (2006).
   
• "Research on Electro-Organic Reactions and Redox-Active Biomolecules", Rusling, J. T.; Fry, A. J., Interface, 15, 59, (20060.
   
• "Electrochemical Techniques" McGraw-Hill Yearbook of Science and Technology, Fry, A. J. and Laitinen H., 10th ed., McGraw-Hill, New York (2006).
   
• "Electrochemical Techniques" McGraw-Hill Encyclopedia of Science and Technology, Fry, A. J., 10th ed., McGraw-Hill, New York (2006).
   
•  “A Computational Study of Solution Effects on the Disproportionation of Electrochemically Generated Polycyclic Aromatic Hydrocarbon Radical Anions”, Fry, A. J., Tetrahedron, 62, 6558 (2006). 
   
• “Construction of Electrocatalytic Electrodes Bearing the Triphenylamine Nucleus Covalently Bound to Carbon. A Halogen Dance in Protonated Aminotriphenylamines”, Mayers, B. T.; Fry, A. J., Organic Letters,  8, 411 (2006).
   
• "Electrophilic Nitration of Triphenylamines a s Route to High Oxidation Potential Electrocatalysts. Polynitration, Nitrodebromination, and Bromine Dance.", Wu, X.; Dube, M.A.; Fry, A. J., Tetrahedron Lett., 47, 7667 (2006).
   
• “Disproportionation of Arene Radical Anions is Driven Overwhelmingly by Solvation, Not By Ion Pairing”,  Fry, A. J., Electrochemistry Communications, 7, 602-606 (2005).
   
• “Further Studies on the Reduction of Benzylic Alcohols by Hypophosphorous Acid/Iodine”, Gordon, P. E.; Fry, A. J.; Hicks, L. D., Arkivoc, 6, 393 (2005).
  
  "Ab Initio Computation of Electron Affinities of Substituted Benzalacetophenones (Chalcones). A New Approach to Substituent Effects in Organic Electrochemistry", Hicks, L. D.; Fry, A. J.; Kurzweil, V. C., Electrochimica Acta, 50, 1039 (2004).
  

• "Strong Ion-Pairing Effects in a Room Temperature Ionic Liquid", Fry, A. J., J. Electroanal.Chem., 546, 35 (2003).
   

• "Anodic Oxidation of  Methyl a-Deimethylsilyldihydocinnamate. A Novel Silicon Gamma-Aryl Effect:, Kaimakliotis, C; Fry, A. J., J. Org Chem., 68, 9893 (2003).

Education

B.S.   1958 University of Michigan

Ph.D. 1963 University of Wisconsin

[Chemistry][Wesleyan]
 
Last updated: August 3, 2009 (AJF/rncb)