(Sp)-(+)-Spiniferin-1 and (Rp)-(−)-spiniferin-1, a pair of unusual marine natural products with planar chirality, were firstly synthesized via a polyfluoroalkanosulfonyl fluoride induced homoallylic carbocation rearrangement reaction. The chiral resolution and palladium-catalyzed β-H elimination of allylic alcohol derivatives were considered as the key steps of these divergent syntheses.

A Grignard reagent induced tandem semipinacol rearrangement/chelation-controlled ketone addition process, which converts 20S-hydroxy-5α-pregnane-16(17)-epoxide into an unusual C20-substituted 17S-pregnane-3S,16R,20S-triol, is described.

19-O-Acylation was found to be indispensable for 1,2-dehydrogenation of 19-hydroxyandrost-4-ene-3,17-dione 1a with DDQ as an oxidant after exploring a variety of C-19 substituents. 1,2-Dehydrogenation in combination with subsequent A-ring aromatization via retro-aldol reaction provided a flexible and efficient protocol for the synthesis of estrogens. To demonstrate the utility of the protocol, pharmaceutically attractive estrogens were synthesized from easily available 19-hydroxy-4-ene-3-keto steroids.

(Sp)-(+)-Spiniferin-1 and (Rp)-(−)-spiniferin-1, a pair of unusual marine natural products with planar chirality, were firstly synthesized via a polyfluoroalkanosulfonyl fluoride induced homoallylic carbocation rearrangement reaction. The chiral resolution and palladium-catalyzed β-H elimination of allylic alcohol derivatives were considered as the key steps of these divergent syntheses.