INTERESTS The main thrust of my research is in the synthesis and study, including theoretical calculations, of theoretically interesting molecules. Areas of current interest include: the search for a neutral homoaromatic hydrocarbon, pyramidalized carbon-carbon double bonds, structurally interesting organic radicals, and highly distorted novel aromatic molecules.
NEUTRAL HOMOAROMATICS: Our calculations suggest that several annelated derivatives of semibullvalene will display the elusive property of homoaromaticity. The concept of homoaromaticity was first proposed nearly four decades ago, and although many examples of molecules bearing a charge have been shown to be homoaromatic, to date there is no well accepted example of a neutral homoaromatic molecule. It is obviously an exciting prospect to prepare the first example of a new class of compounds. Success in this area would not only "prove" a long-standing prediction, but also would validate the novel discriminators that we developed for the prediction of homoaromaticity.
PYRAMIDALIZED ALKENES: Calculations predict that certain highly strained bridged polycyclic alkenes will have a non-planar double bond. We are continuing our early work in this area by preparing other novel polycyclic systems. An added attraction to this research is that some of the intermediates on the way to our target molecules will potentially exhibit antiviral activity (the National Cancer Institute has requested that I supply related samples for testing against AIDS and cancer).
NOVEL AROMATICS: Cyclophanes are a most fascinating class of organic molecules. They exhibit interesting properties, such as high p donor ability, low energy electronic transitions and highly distorted aromatic decks. These properties result, in the main, from the large transannular interaction present in cyclophanes. We wish to exploit these properties in the design of a novel conducting polymer. We are currently exploring the synthesis of a novel naphthalenophane and other highly strained naphthalenes which we ultimately hope to coordinate to appropriate transition metals (e.g., ruthenium) to form a new conducting polymer. We are also carrying out theoretical investigations in this area.
I am also interested in the development of new synthetic methods, in particular, utilizing organo-silicon and -sulfur chemistry. Recent work in this area included the development of new ketene, allene and acetylene equivalents for the Diels-Alder reaction. We are also using silicon chemistry to control the Wagner-Meerwein rearrangement in some rigid bicyclic molecules. The goal in this project is to make usually difficultly accessible molecular frameworks readily available. In particular, we wish to use this methodology to set up the required stereochemistry for a second controlled rearrangement (the anionic oxy-Cope rearrangement).