| This dissertation describes the development of a general method for the enantioselective synthesis of angularly substituted 1-azabicyclic ring systems that delivers the product amines in high yields and enantiopurity. A review of methods currently disclosed in the literature for the synthesis of these ring systems reveals that, with the exception of the studies described in this dissertation, only one general method has been reported for the enantioselective synthesis of angularly substituted 1-azabicyclic ring systems. The method developed in this account utilizes a methylene-transfer driven 2-aza-Cope rearrangement, in which a dynamic kinetic resolution of a rapid tautomeric equilibration of diastereomeric iminium ions occurs via a diastereoselective [3,3]-sigmatropic rearrangement. Experiments illustrating the scope of the reaction and studies investigating aspects of the reaction mechanism are described. |
