35 MorphinanおよびB/C trans-morphinanの合成  [in Japanese] 35 Synthesis of Morphinan and B/C Trans-fused Morphinan  [in Japanese]

To the solution of 1,2,3,4-tetrahydrophenanthrene-9-ol (I) in 10% NaOH, CHBr_3 was added to give the enone (II). Two isomers of the bromocyclopropane derivatives (III and III') were obtained by the reduction of II with Fe-AcOH-EtOH. Reaction of these isomers (III and III') with CN^- gave a sole product (IV). Reduction of IV with NaBH_4 or catalytic reduction over Pd-C afforded A/B cis and trans fused alcohols (V and VI). These alcohols were reduced over Raney Ni to aminocompounds and then dehydrated to corresponding unsaturated aminocompounds (XIII and XIV). Cyclization of the compounds (XIII and XIV) to morphinan structures were accomplished treating with NCS and dichlorocompounds (XV and XVI) were obtained. Catalytic reduction of the dichlorocompounds (XV and XVI) gave morphinan and B/C trans-fused morphinan.