抄録
Stereoselective hydrogenolysis of alkenyloxiranes to homoallylic alcohols was carried out using formic acid in the presence of palldium-phosphine catalyst. The stereoselectivity of hydride attack, which induces the ring opening of alkenyloxiranes, can be controlled by the olefin geometry of alkenyloxiranes. Thus, inversion of configuration at the oxirane carbon by the hydride attack was observed in the reaction of (E)-alkenyloxiranes, whereas configuration at the oxirane carbon was retained with (Z)-alkenyloxiranes owing to the anti-syn isomerization of the π-allylpalladium system prior to the hydride attack. On the basis of these observations, syntheses of optically active natural products, (-)-serricornin, (-)-nupharamine, dendrobatid alkaloids 235B, 205A, invictolide, endo-1,3-dimethyl-2,9-dioxabicyclo[3,3,1]nonane, and yashabushitriol were performed.
