Free radical chain reactions will be designed involving electron- accepting and electron-donating alkyl radical additions to unsaturated systems that are both electron-rich and electron- deficient. Both types of radicals will be generated from alkylmercury halides. Reactivities of unsaturated systems toward these radicals will be established from product analysis by competitive reactions. Demonstration of enhanced reactivity in electron transfer reactions of radicals will be an important goal of this research. Complexation with nucleophiles has already been demonstrated to increase the electron-donating ability of alkylmercury halides and similar nucleophilic solvent complexation with paramagnetic species such as silyl radicals will be used to increase electron transfer to an easily reduced molecule. The concept of radical activation in electron transfer processes by protonation or deprotonation will continue to be pursued, particularly in regard to the alkylation of aromatic systems. %%% This grant from the Organic Dynamics Program supports the continuing work of Professor Russell at Iowa State University. The formation carbon-carbon bonds is a process of considerable importance in organic chemistry. One method by which the formation of carbon-carbon bonds is initiated is the addition of a carbon free radical (a trivalent carbon with one odd electron) to a carbon-carbon double bond. Only recently has the synthetic utility of this reaction been vigorously pursued. In this research, new methods will be developed to facilitate this addition reaction. A scale of reactivity of free radical addition to carbon-carbon double bonds will be developed and this will serve as a guide for the synthesis of organic molecules.
