Synthesis and reactivity of Fischer chelate carbene complexes: Application to indole alkaloid synthesis

This thesis describes the synthesis of chiral and achira oxazolidinone and imidazolidinone chelated Fischer carbene complexes. These carbene complexes are used in the development of the first examples of an enantioselective cyclohexadienone reaction. These reactions are shown to proceed with diastereomeric excesses greater than 95%.; This stereoselective cyclohexadienone reaction is then applied as the key reaction in a partial synthesis of the important indole alkaloid vindoline.; The benzannulation reactions of simple phenyl carbene complexes with imidazolidinone and oxazolidinone heteroatom groups was also investigated. These novel carbene complexes react with terminal alkynes to produce unusual "two-alkyne" annulation products.; Additionally, the benzannulation chemistry of {dollar}beta,beta{dollar}-disubstituted aromatic carbene complexes is reviewed.