First Total Synthesis of Enantiomerically Pure(−)‐Silphiperfol‐6‐en‐5‐on

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Abstract
The angular triquinane (−)‐silphiperfol‐6‐en‐5‐on ((−)‐14) has been synthesized for the first time time in enantiomerically pure form. A highly efficient triplet‐sensitized photoreaction, the oxadi‐π‐methane rearrangement of the complex β,γ‐enone(+)‐6 to (−)‐7, constitutes the key step. The know staring material, (1R, 7aR)‐3,6,7,7a‐tetrahydro‐1‐hydroxy‐7a‐methyl‐1H‐inden‐5(2H)‐one ((−)‐2), is readily accessible in > 97% enantiomeric purity. This new approach should enable access also to other angularly fused triquinanes of the silphinene type and related structures.