Studies toward the enantioselective synthesis of the gelsemium alkaloids

Developments in catalysis using late transition metals, such as gold and platinum, have provided an abundance of transformations that are useful to the organic chemist. The unique alkynophilic properties of these metal catalysts is a consequence of relativistic effects, which allows these metals to function in reactions as more than just a Lewis acid. Herein, we sought to discover new modes of reactive nucleophilic partners for ,-unsaturated platinum carbenes, in particular, nucleophiles which also contained a heteroatom. In addition, we were interested in converting our previous racemic synthesis of gelsenicine into an enantioselective synthesis by utilizing a chirality transfer approach. Two generations of substrates were created in order to see if such a strategy would prove successful.