26 三員環の選択的開裂を経由する核間位への官能基を有する炭素化法

抄録

Various substituted methyl groups were introduced into an angular position of tricyclic phenoles via ring opening of cyclopropanes. Ring opening reactions underwent selectively to give the most stable anionic intermediates. Formation of cyclopropanes Reaction of 1,1-dimethyl-1,2,3,4-tetrahydrophenanthrene (I) with CHBr_3 in aquaous NaOH gave the enone (II). Reduction of II with Zn-AcOH or Li-NH_3 or catalytic reduction over Pd-C afforded the bromo cyclopropane (III) which was characterized by the infrared (IR) spectrum and the nuclear magnetic resonance (nmr) spcetrum and by hydrogenolysis to cyclopropanes. Angular formylation Acetolysis of bromocyclopropane (VI) led to the acetoxy cyclopropane (VII) in a good yield. VII was hydrolized into 4a-formyl compound (IX). Angular cyano methylation, nitromethylation and sulfonomethylation Bromocyclopropane (III) reacted with KCN, NaNO_2 and NaSO_2Ar in DMSO to give (XIII), (XIV) and (XV) respectively in a good yield. Substituted cyclopropanes Bromocyclopropane (III) reacted with CH_3OH, CH_3CO_2H, NH(CH_3)_2 NaN_3 and NaSBz to afford (XVI) (XVII) (XVIII) (XIX) and (XX) respectively which were characterized by IR spectra and nmr spectra. Ring opening of substituted cyclopropanes Substituted cyclopropanes were treated with bases. (XVI), (XVII) and (XX) gave (XXVII) (XXII) and (XXVI) respectively.