Part~I. Total synthesis of epibatidine homologs. Part~II. Nitrogen insertion reactions of bridged bicyclic ketones: A: Substitutent effects on the regiochemistry of the Schmidt reaction of 7-substituted bicyclo(2.2.2)heptan-2-ones. B: Attempted regiose

art I. Epibatidine, an alkaloid found in the skin of Epipedobates tricolor frog, is one of the most potent analgesics described to date. It has been found to be 200-500 times as potent as morphine, but it has a very narrow margin of safety. Further work on epibatidine related structures may provide useful compounds for study of nicotinic receptors in the brain. We have synthesized epibatidine homologs: (;Part II. A: The Schmidt reaction of bicyclo (2.2.1) heptan-2-one affords methylene migrated (NM) lactam in addition to cleavage products. The Schmidt reactions of 7-anti and syn substituted bicyclo (2.2.1) heptan-2-ones give both methylene migration (NM) and bridgehead migration (NBH) products. The results are consistent with rearrangements occurring via iminodiazonium ions but not tetrahedral protonated azidohydrins.;Part II. B: Attempts to control the regiochemistry of nitrogen insertion in the Barton modification of the Beckmann reaction using...