Bridged Polycyclic Compounds. 87. Radical Rearrangements in Some Bicyclooctadienyl, Tricyclooctenyl, Bicyclononatrienyl, and Tricyclononadienyl Systems

Article abstract of DOI:10.1021/jo00337a034

Chlorides and S-methyl xanthates of alcohols in the chlorobenzobicyclo<3.2.1>octadienyl systems 1 and 2, the chlorobenzobicyclo<2.2.2>octadienyl system 3, the chlorobenzotricyclo<3.2.1.0^2,7>octenyl systems 7 and 8, the chlorodibenzobicyclo<3.2.2>nonatrienyl systems 23-25, the chlorodibenzotricyclo<3.3.1.0^2,8>nonadienyl system 26 and the dibenzobicyclo<2.2.2>octadienyl system 30 have been treated with tri-n-butyltin and/or triphenyltin hydrides.Replacement of the functional group (chlorine or xanthate) by hydrogen proceeds through a radical intermediate which may, depending upon its nature and/or experimental conditions, rearrange before capture by hydrogen transfer.Comparison of these radical intermediates with each other and with corresponding carbocations is discussed briefly.The intervention of an alkoxythiocarbonyl radical in the xanthate reduction has been demonstrated.