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

(860) 685-2622
afry@wesleyan.edu

Organic Chemistry: Synthetic and Mechanistic organic electrochemistry; metal-ion and metal complex mediated organic electrode reactions; electrochemical behavior of benzenoid and non-benzenoid aromatic hydrocarbons; electrochemically-driven enzymatic synthesis of amino acids. 

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

Education

B.S.   1958 University of Michigan
Ph.D. 1963 University of Wisconsin


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