Synthetic applications of the type 2 intramolecular Diels-Alder reaction: (1) Efforts toward the total synthesis of the welwitindolinone alkaloids and (2) Enantioselective synthesis of bridged bicyclic ring systems

This dissertation describes the synthesis of an advanced welwitindolinone intermediate via an alkylation/cyclization cascade reaction. This cascade reaction prepares a highly functionalized welwitindolinone core structure containing two all--carbon quaternary centers, sets two stereocenters, and assembles all but two carbon atoms of the B and C welwitindolinone skeleton from simple materials in short fashion. Additionally, a novel route for the preparation of 4-vinyl oxindoles via the Suzuki cross-coupling reaction is described. In another project, asymmetric variants of the type 2 intramolecular Diels--Alder reaction incorporating oxazolidinone chiral auxiliaries were evaluated. This study has resulted in systems that deliver bridged bicyclic [5.3.1] and [4.3.1] ring systems in high diastereomeric (97-99% de)(and enantiomeric) purity.