The first chapter describes a successful attempt to rigorously prove the absolute stereochemistry of the isopavinane alkaloids by synthesis of an optically active member of this group from an intermediate of known absolute configuration. The second chapter briefly reviews the phenethyl-isoquinoline alkaloids and describes the synthesis of novel phenethylisoquinoline derivatives which are homologues of the isopavinane alkaloids. Although these "homoisopavinanes" have not been found to occur naturally to date, it is the author's belief that they represent a highly probable alkaloid class. Intramolecular oxidative aryl-aryl coupling of phenolic and non-phenolic substrates plays an important role in the biosynthesis and synthesis of a number of alkaloids and other polycyclic compounds. Recently a number of reports describing the use of vanadium oxytrifluoride as an efficient reagent for effecting such oxidative couplings have appeared. For several years, workers in this laboratory have been trying to devise an efficient synthetic route to isomers of the aporphine alkaloids based on the dibenz [de,g] isoquinoline system. The final chapter of this thesis briefly reviews oxidative coupling with particular emphasis on the use of vanadium oxytrifluoride and describes the successful application of this reaction to the synthesis of two isomers of the aporphines based on the dibenz [de,g] isoquinoline system. Attempts to isolate a postulated intermediate in these reactions are also described. Finally, the successful application of this oxidative coupling reaction to the synthesis of a 9-aminophenanthrene derivative is described.
|Date of Award||1978|