Spiniferin-1, a rare planar chiral natural product with a 1,6-methano[10]annulene skeleton, has been synthesized via a novel polyfluoroalkanosulfonyl fluoride induced cascade carbocation rearrangement reaction. Natural spiniferin-1 was established as a racemic mixture by comparing its specific rotation with those of our synthesized S p -(+)-spiniferin-1 and its R p -(-)-enantiomer.

3-Aminoestrogens are promising estrogen drugs. Traditional synthesis of the estrogens used estrone as a raw material, however, was not suitable for diversity-oriented synthesis. Herein, an efficient synthesis of 6-substitued-3-aminoestrogens from easily available 19-hydroxy-androst-4-ene-3,17-dione via a tandem retro-aldol aromatization/intermolecular nucleophilic addition is presented. The method featured easily available reagents, simple operation and introduction of two substituents in one step.