New Directions for Bis-Adamantane Chemistry and Reactivity

Bulky chiral ligands have gained tremendous attention in metal coordination chemistry as they influence greatly coordination geometry and reactivity and are critical features of asymmetric catalysts. In this thesis, the design and synthesis of sterically congested chiral alcohol and amine ligands based on a bis-adamantane framework, are explored. Optimization of the ligand synthesis and purification were conducted on the racemic ketone, while the chiral synthetic pathway utilized an enzymatic hydrolysis as the key step. In another aspect of bis-adamantane chemistry, the bromonium ion of adamantylideneadamantane (Ad=Ad) has provided valuable mechanistic information about electrophilic addition of bromine and undergoes a fast “Br+” transfer process to alkenes. However, the Ad=Ad isomer SesquiAdAd only reacts with [AdAdBr+] and not with Br2. This thesis also investigated the rearrangement of SesquiAdAd to Ad=Ad catalyzed by [AdAdBr+] via the formation of the potentially high energy intermediate SesquiAdAdBr+, probed by 1H NMR spectroscopy and kinetics. Data analysis involved a series of 1H NMR spectral deconvolutions.