My research interests have ranged widely over the years. As a graduate student at the University of Wisconsin (Ph.D. in 1967), my main interest was in physical organic chemistry. I worked under the direction of Professor David Lemal (now at Dartmouth College), investigating the properties of highly strained hydrocarbons. My thesis and my first publication concerned the synthesis and some of the chemistry of "hexamethylprismane"; J. Am. Chem. Soc., 1966, 88, 5934. Since then, I've explored a range of mechanstic and synthetic problems, some of which are described here in reverse chronological order.
In 2002 the Lawrence departments of chemistry and biology received a 3-year grant from the Merck Foundation to fund interdisciplinary research project. I have been involved in two of those.
1. With Bart De Stasio, Nancy Wall, and Beth De Stasio of the biology department and six students:
Biochemical Analysis of Kairomones and Developmental Biology of Inducible Defenses in Cladocera
2. With Brad Rence and several students:
Behavioral, Anatomical, Physiological and Biochemical Aspects of Pheromonal Sex Recognition in the House Cricket, Acheta domesticus (L.)
In the late 70s and early 80s, I became interested in chemical communication, and especially in defensive uses of chemical compounds by insects. That included work on a synthetic route to the compound Pederin, a highly irritating material secreted by a rove beetle, supported initially by a small grant from the Research Corporation, and later by another grant from the Petroleum Research Fund administered by the ACS and by two smaller grants from the Monsanto Chemical Company..
Approaches to a Total Synthesis of Pederin and related projects
My Ph.D. work, as mentioned above, was focused on the synthesis and properties of strained hydrocarbons, and culminated in the synthesis of hexamethylprismane.
Following the completion of that work, I did a short post-doctoral research stint in the laboratory of Professor Glen Russell at Iowa State University, looking primarily at the ESR spectra of alpha-keto radicals. These I prepared primarily by oxidation of enolate anions with Ceric ion in ESR flow cells. That project produced two papers: "alpha-Keto Radicals," with G. A. Russell, J. Am. Chem. Soc., 1967, 89, 5059, and "Application of Electron Spin Resonance Spectroscopy to Studies of Valence Isomerization. II. Bicyclo[4.1.0]-heptene-2,5-semidiones," with G. A. Russell and T. Ku, J. Am. Chem. Soc., 1970, 92, 3833.
Several students worked on some other small strained hydrocarbons in my first few years at Lawrence, primarily in an exploration of some small compounds for which Paul Gassman (at about that time) coined the term “twisted cyclopropanes.” These were tricyclic compounds in which two small rings were fused to a central cyclopropane. The general formula and a particular compound we looked at are shown below. ("Decomposition of a beta,gamma-Unsaturated Diazo Ketone: Evidence for the Intermediacy of a Bicyclopentanone," with J. O'Dea* and E. A. Hill, J. Org. Chem., 1974, 39, 3355.)
An interest in getting some practice in synthetic chemistry, and some common interests in diazoketones, took me to the laboratory of Professor Peter Yates at the University of Toronto for a sabbatical leave in 1973-74. That visit also resulted in two papers: "Preparation and Spectra of Mercuribis(alpha-Diazo Ketones)," with P. Yates and F. X. Garneau, Tetrahedron, 1975, 31, 1979, and "Diels-Alder Adducts of 6-Heterosubstituted Fulvenes," with P. Yates, Synth. Comm., 1975, 5, 37.
Finally, a variety of other projects have been carried out by students in my laboratory over the years, some of them at my suggestion, and some because the students themselves brought interesting experimental questions to me. Some have been converted into course laboratory projects, others have been presented at various undergraduate research symposia on campus or elsewhere. I continue to be interested in processes that can be followed by NMR, by mechanistic puzzles, by synthetic challenges, and a host of other possibilities.
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