SYNTHESYS OF HETEROCYCLIC PROPELLANES. PREPARATION AND TRANSANNULAR REACTIONS OF 5-ETHOXYCARBONYLMETHYLENE-CYCLOOCTANONE AND CORRESPONDING OXIMES AND HYDRAZONES

Article abstract of DOI:10.1016/S0040-4020(01)88060-1

5-Ethoxycarbonylmethylene-cyclooctanone (3) is prepared by Wittig monoolefination of dione 1 with phosphorus ylide 2.Thermal transannular cyclization of oxime 6 and phenylhydrazone 12 of the ketone 3 affords 3-oxa-2-aza- and 2,3-diaza<3.3.3>propellanes 7 and 14 respectively.Irradiation of ketone 3, its oxime 9, and its dimethylhydrazone 16 furnish 9-oxa-, and 9-aza<3.3.2>propellanes 11, 10, and 17, respectively.In addition to the propellane 14, phenylazobicyclo compound 13 is also obtained from phenylhydrozyne 12.The acetyl derivatives 8 and 15 of propellanes 7 and 14 are also prepared and studied.