This grant from the Organic Dynamics Program supports the work of Dr. Alex Nickon at the Johns Hopkins University. This investigation will afford new insights into the structure and reactivity of highly reactive chemical intermediates. The experiments that will be carried out by Dr. Nickon will center on rearrangements of carbenes to alkenes. The study will employ reactants that are doubly labelled with carbon and deuterium to evaluate stereoelectronic requirements for the rearrangements. The research will also focus on the photochemical rearrangement of alkenes to carbenes, a process that is the reverse of the normally observed pathway. This rearrangement is believed to proceed via Rydberg excited states, which may have partially twisted geometries. This reaction of strained reactants may provide a method for direct access to anti-pyramidalized alkenes.
