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

We have two major projects underway at present. In one, we are studying the reactions of hydrogen iodide generated catalytically by hypophosphorous acid and a trace of iodine in acetic acid. A wide variety of conversions can be carried out in high yield by this system, including reductive deozygenation of ketones and alcohols to alkanes, selective reduction of the double bond of unsaturated ketones, reduction of the double bond of substituted stilbenes, and dehalogenation of alkyl halides. Substitution of deuteriohypophosphorous acid results in polydeuteration; for example, up to ten deuterium atoms can be introduced into the bibenzyl derived by reduction of stilbene with this system. The reactions apparently take place by a combination of radical and ionic pathways which are being actively investigated. We are attempting to develop an electrocatalytic version of this chemistry, in which an electrode supplies current to replace the hypophosphorous acid; if successful, this will lead to a variety of new electrocatalytic processes.

The other project involves a study of the chemistry and anodic electrochemistry of silylated compounds such as 1,2-disiylethanes and alpha-dimethylsilyl carbonyl compounds.. Carbanions can be generated by reaction of these substances with fluoride ion, or they can be oxidized electrochemically to create organic cations.
    
  Selected Publications

• "Cross-linked LDH Crystals for Lactate Synthesis Coupled to Electroenzymatic Regeneration of NADH", S. B. Sobolov, M. D. Leonida, A. Bartoszko-Malik, F. McKinney, J. Kim, K. I. Voivodov, A. J. Fry, J. Org. Chem. 61, 2125 (1996).
   
• "Solvents and Supporting Electrolytes", A. J. Fry, in Laboratory Techniques in Electroanalytical Chemistry, 2nd ed., P. T. Kissinger and W. R. Henieman, eds., Marcel Dekker, (1996).
   
• "Electrochemical Formation and Dimerization of Alpha-substituted Benzyl Radicals. Steric Effects on Dimerization", A. J. Fry, J. M. Porter, P. F. Fry, J. Org. Chem. 61, 3191 (1996).
   
• "Equilibrium Acidities and Homolytic Bond Dissociation Enthalpies of the Acidic C-H Bonds in P-(p-Substituted Benzyl)triphenylphosphonium Cations and Related Cations", X.-M. Zhang, A. J. Fry, F. G. Bordwell, J. Org. Chem. 61, 4101 (1996).
   
• "Co-Electropolymerization of a Viologen Oligomer and Lipoamide Dehydrogenase on an Electrode Surface. Application to Cofactor Regeneration", M. L. Leonida, A. J. Fry, S. B. Sobolov, K. I. Voivodov, Bioorg. Med. Chem. Lett. 6, 1663 (1996).
   
• "Cobalt(salen)-Electrocatalyzed Conversion of Benzotrichloride to Tolane. A Quintuple Electrochemical Transformation", S. A. Kaufman, T. Phanijphand, A. J. Fry, Tetrahedron Lett. 37, 8105 (1996).
   
• "The Electrochemistry of Nitro, Nitroso, and Related Compounds" A. J. Fry in The Chemistry of Amino, Nitroso, Nitro & Related Groups, Supplement F2, S. Patai, ed., Wiley, New York, p. 837 (1997).
   
• "The Electrochemistry of the C=C, C=O, and C=N Groups" A. J. Fry in The Chemistry of Double-bonded Functional Groups, Supplement A3, Wiley, New York, p. 611 (1997).
   
• "Stereoselective Electrochemical and Chemical Reductive Silylation of Bicyclic Geminal Dihalocyclopropanes. Effects of Ultrasound" A. J. Fry, J. Touster, Electrochemica Acta 42, 2057 (1997).
   
• "Bond Dissociation of Antioxidants" Q. Zhu, X.-M. Zhang, A. J. Fry, Polymer Degradation and Stability 57, 2444 (1997).
   
• "New Biopolymers for Electroenzymatic Synthesis of Alpha-Hydroxy Acids" A. J. Fry, S. B. Sobolov, M. D. Leonida, K. I. Voivodov, J. M. Fenton, in Fundamentals and Potential Applications of Electrochemical Synthesis, R. D. Weaver, F. Fisher, F. R. Kalhammer, D. Mazur, eds., Electrochemical Society, Pennington, NJ, p. 115 (1997).
   
• "Stereoselective Sonochemical Reductive Silylation of Geminal Dibromocyclopropanes by Bulk Magnesium" J. Touster, A. J. Fry, Tetrahedron Lett. 38, 6553 (1997).
   
• "1,2-Bis-Trialkylsilylethanes: Synthons for Vicinal Dications?" J. M. Porter, X. Xuan, B. Blackman, D. Hsu, A. J. Fry, Tetrahedron Lett.38, 7147 (1997).
   
• "Discrete High Molecular Weight Triarylamine Dendrimers Prepared by Palladium-Catalyzed Amination", J. Louie, J. F. Hartwig, A. J. Fry, J. Am. Chem. Soc. 119, 11695 (1997).
   
• "FAD-Mediated Enzymatic Conversion of NAD+ to NADH: Application to Chiral Synthesis of L-Lactate", M. D. Leonida, S. B. Sobolov, A. J. Fry, Bioorg. Med. Chem. Lett.8, 2819 (1998).
   
• "Synthesis, Chemistry, and Anodic Oxidation of 1,2-Bis(trialkylsilyl)ethanes" in S. Torii, ed., Novel Trends in Electroorganic Synthesis, Springer-Verlag, Tokyo, p. 109 (1998).
   
• "Stereoselective Ultrasonically-Induced Reductive Monosilylation of Geminal Dibromonorcaranes. Steric Effects", B. C. Raimundo, A. J. Fry, J. Organomet. Chem., 584, 230 (1999).
   
• "Electrochemical Synthesis in Microemulsions. Direct and Catalyzed Reductions", H. Carrero, J. Gao, J.F. Rusling, C.-W. Lee, A. J. Fry, Electrochimica Acta, 45, 503 (1999).
   
• "Convenient Synthesis of a Reactive Ester Homoenolate" E. DiMauro, A. J. Fry, Tetrahedron Lett., 40, 7945 (1999).
   
• "Hypophosphorous Acid-Iodine: A Novel Reducing System. I. Reduction of Diaryl Ketones to Diaryl Methylene Derivatives" L. D. Hicks, J. K. Han, A. J. Fry, Tetrahedron Lett., 41, 7817 (2000).
   
• "Anodic Oxidation of Stilbenes" A. J. Fry, F. Akinfaderin, B. Blackman, S. Halas, B. Mayers, K. Okyne, L. Rodman, in A. J. Fry (editor), New Directions in Organic Electrochemistry, Electrochemical Society, Pennington, NJ, p. 41 (2000).
   
• "Hypophosphorous Acid-Iodine:  A Novel Reducing System. II. Reduction of Benzhydrols to Diarylmethylene Derivatives", Gordon, P. E.; Fry, A., J. Tetrahedron Lett.,  42, 831 (2001).
   
• "Dual Reaction Pathways in the  Magnesium-Mediated Synthesis of Aziridines from Benzal Halides and Imines", Biscoe; M. R..; Fry, A.,
  J. Tetrahedron Lett., 42, 2759 (2001).
   
• "Fluoride-Promoted Reactions of Unsaturated Carbonyl Compounds. Dimerization by a Non-Bayliss-Hillman Pathway", Judy X. Xuan, J. X.;
   Fry, A. J.  Tetrahedron Lett., 42, 3275 (2001).
   
• "Reactions Cascase in the Anodic Oxidation of Benzyl Silanes in Methanol", Taylor, K.; Miura K.; Akinfaderin, F.; Fry A. J. , J. Electorchem. Soc., 150, D85 (2003).
   
• "Synthesis, NMR Spectroscopy, and Conformational Analysis of alpha-Dimethylsilyl Esters", Kaimakliotis, C.; Arthanari H.; Fry, A.J. ,
  J. Organomet. Chem., 671, 126 (2003).
   
• "Anodic Oxidation of Negatively Substituted Stilbenes", Halas, S.M.; Okyne, K.; Fry, A.J., Electrochimica Acta, 48, 1837 (2003).
   
• "Strong Ion-Pairing Effects in a Room Temperature Ionic Liquid", Fry, A.J., J. Electroanal.Chem., 546, 35 (2003).
   
• "Novel Desilylation of alpha-Dimethylsilyl esters by Electrochemically Generated Superoxide Ion", Kaimakliotis, C.; Fry, A.J., Tetrahedron Letters,  44. 5859 (2003).
   
• "Electrochemical Oxidation and Reduction of alpha-Dimethylsilyl Esters. A Novel Silicon Gamma-Effect", in Mechanistic and Synthetic Aspects of Organic and Biological Electrochemistry", D.G. Peters, J. Simonet, and H. Tanaka, Eds.,  Fry, A.J.; Kaimakliotis, C., The Electrochemical Society, Inc., Pennington, NJ, 77-80 (2003).
   
• "Anodic Oxidation of Methyl a-Dimethylsilydihydrocinnamate. A Novel Silicon Gamma-Aryl Effect", Kaimakliotis, C.;  Fry, A.J.,  J. Org. Chem., 68, 9893 (2003).
   
• "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).
   
• "Electrochemical Processes", Fry, A. J., (review) in the Kirk-Othmer Encyclopedia of Technology, 10th edition (this, as all subsequent editions will bre, is on-line), July (2004).
   
• “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).
   
• “Disproportionation of Arene Radical Anions is Driven Overwhelmingly by Solvation, Not By Ion Pairing”,  Fry, A. J., Electrochemistry Communications, 7, 602-606 (2005).
   
•  “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).
   
• "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).
   
• "Electrophilic Nitrodebromination, and Bromine Dance.", Wu, X.; Dube, M.A.; Fry, A. J., Tetrahedron Lett., 47, 7667 (2006).
   
• "Experimental/Computational Study of the Electrochemical Oxidation of Cyclooctatetraene in Protic Media. Solvent Effects.", Connors, G.; Wu, X.; Fry, A. J., Organic Letters,  9, 1671(2007).

 

• "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 Examination of Substituent Effects on the Interconversion of 1.3.5- Cyclooctatriene and Bicyclo[4.2.0]-2.4-octadiene." Tetrahedron, 64, 2102 (2008).

  Education
  

  B.S. 1958 University of Michigan

  Ph.D. 1963 University of Wisconsin
  
  

  
  [Chemistry][Wesleyan]
   
  Last updated: August 15, 2008 (AJF/rncb)