Experimental and computational investigations of substituent effects on housane cation radical rearrangement, intramolecular atom transfer reactions of trimethylenemethane diradicals, and kinetic isotope effects on alkylidene carbene insertion reactions

New synthetic routes to substituted housane (bicyclo[2.1.0]pentane) compounds have been devised and the electron-transfer catalyzed rearrangement of some 2-aryl and 2-(trimethylsilylmethyl) housanes have been investigated. Ab-initio and semi-empirical computational models of the reactive intermediates and transition states were constructed to aid in determining the mechanism leading to the observed products. Computational studies were performed on trimethylenemethane-type diradicals with tethered hydrogen, halogen, and other groups to attempt to rationalize experimental results and provide a framework to predict which potentially synthetically useful transfers would proceed. Alkylidene carbenes capable of undergoing either intramolecular addition to an olefin or insertion into a C-H bond were synthesized and their relative reactivities determined. Deuterated analogs were then synthesized to probe the kinetic isotope effect of the insertion reaction.