AREA UNDER CONSTRUCTION. See "Current Research and Publications" for a list of papers and recent abstract figures
General Overview:
We are interested in inventing new reactions and studying reactive intermediates. In particular, we creating novel molecules using oxocarbenium ion and iodonium ion intermediates in cascade, or domino reaction sequences. These complex processes involve a number of discreet organic transformations in which the individual reactions must take place in a specific order for the overall reaction to afford products in reasonable yields. In essence, one reaction (domino) must fall (react) before the next reaction can proceed, and so-on.
Prins chemistry:
The Prins reaction was first described 100 years ago and is the result of attack of an activated ketone or aldehyde by an alkene followed by trapping by a nucleophile. In the last two decades, it has become increasingly important in the synthesis of tetrahydropyran and dihydropyran ring systems, which are prevalent in many anticancer, antifungal and antibiotic compounds. We began this area of research using catalytic quantities of BiX3 (X = Br, Cl, OTf) using an intramolecular cyclization/nucleophilic addition strategy in collaboration with P. Andrew Evans, now at Queen’s University in Ontario. This cyclization creates an incipient oxocarbenium ion to which an alkene or silane nucleophile can add. At about this time, a paper appeared in which an alkyne was used to trap the intermediate oxocarbenium ion and we have been investigating this ever since. Please see below for publications and reaction abstracts.
Polyyne Syntheses and Bioactivity:
In collaboration with Doug Young, also in Chemistry at W&M, we recently published a study of simple diynes and their effects on bacterial cell cultures. Rather than examine derivatives of naturally-occurring diynes, we synthesized simpler analogues to determine the structural features that might be necessary for biological activity. We are currently pursuing funding to continue this work.