13,14-Seco-steroids: A New Type of Modified Steroids Containing a Nine-Membered Ring

Oxidations of 14α-hydroxy-5α-cholestan-3β-yl acetate ( 5 ) with lead tetraacetate under thermal or photolytic conditions or in the presence of iodine proceed mainly by fragmentation of the C(13)−C(14) bond to give as the primary products the 13,18-didehydro-13,14-seco derivative 6 and the (E )-Δ¹²-13,14-seco ketone 11 , respectively. Further transformations of these compounds under conditions of their formation afforded, in addition, the acetoxy derivatives 7 – 9 (from 6 ), and the D-homo-C-nor compound 12 and (12R,13R)-epoxide 13 (from 11 ). Unexpectedly, the photolytic lead-tetraacetate oxidation of 5 resulted partly (to ca. 20%) in a reversible fragmentation involving scission and recombination of the C(8)−C(14) bond followed by formation of the 14β,22-ether 10 . Possible mechanisms for the observed transformations are discussed.