| Chapter one. The purpose of this work was to apply a newly developed technique, electrospray ionization mass spectrometry (ESI-MS), to organic chemistry. By introducing a crown ether binding site into a diene, dienophile or dipolarophile, their solution chemistry was explored. An effective method to determine structures of vitamin D and its metabolites by ESI-MS was developed. The dienophilic reactivity of buckminsterfullerene {dollar}rm Csb{lcub}60{rcub}{dollar} was studied by monitoring the course of reactions using ESI-MS. The accuracy of employing ESI as a quantitative analytical method was investigated. Efficient syntheses of the crown diazo reagent and the tagged {dollar}rm Csb{lcub}60{rcub}{dollar} were developed in order to facilitate the study of {dollar}rm Csb{lcub}60{rcub}{dollar} chemistry and mass analysis of {dollar}rm Csb{lcub}60{rcub}{dollar} derivatives. Our studies suggest that ESI-MS is a powerful tool for studying many aspects of organic chemistry.; Chapter two. The chemistry of fullerene {dollar}(rm Csb{lcub}60{rcub}){dollar} was studied through the functionalization of {dollar}rm Csb{lcub}60{rcub}{dollar} via (2+4), (2+3), (2+2) and ene reactions. Several methods for introducing functional groups into the cycloadducts have been developed in order to prepare {dollar}rm Csb{lcub}60{rcub}{dollar} derivatives with desired chemical or physical properties. Some fullerene derivatives so prepared exhibited significant anti HIV-1 activity and low toxicity.; The (2+3) cycloaddition of substituted diazo compounds to {dollar}rm Csb{lcub}60{rcub}{dollar} yields both kinetic and thermodynamic addition products. Thermal and photochemical rearrangements of these adducts were performed and a mechanism was proposed.; Stereoselective Diels-Alder reactions of {dollar}rm Csb{lcub}60{rcub}{dollar} were investigated. Three approaches have been explored and enantiomerically pure {dollar}rm Csb{lcub}60{rcub}{dollar} cycloadducts were synthesized. |
