Oxidative Fragmentations of the 5α- and 5β-Hydroxy-B-norcholestan- 3β-yl Acetates

Oxidations of 5α‐hydroxy‐B‐norcholestan‐3β‐yl acetate (8) with Pb(OAc)4 under thermal or photolytic conditions or in the presence of iodine afforded only complex mixtures of compounds. However, the HgO/I2 version of the hypoiodite reaction gave as the primary products the stereoisomeric (Z)‐ and (E)‐1(10)‐unsaturated 5,10‐seco B‐nor‐derivatives 10 and 11, and the stereoisomeric (5R,10R)‐ and (5S,10S)‐acetals 14 and 15 (Scheme 4). Further reaction of these compounds under conditions of their formation afforded, in addition, the A‐nor 1,5‐cyclization products 13 and 16 (from 10) and 12 (from 11) (see also Scheme 6) and the 6‐iodo‐5,6‐secolactones 17 and 19 (from 14 and 15, resp.) and 4‐iodo‐4,5‐secolactone 18 (from 15) (see also Scheme 7). Oxidations of 5β‐hydroxy‐B‐norcholestan‐3β‐yl acetate (9) with both hypoiodite‐forming reagents (Pb(OAc)4/I2 and HgO/I2) proceeded similarly to the HgO/I2 reaction of the corresponding 5α‐hydroxy analogue 8. Photolytic Pb(OAc)4 oxidation of 9 afforded, in addition to the (Z)‐ and (E)‐5,10‐seco 1(10)‐unsaturated ketones 10 and 11, their isomeric 5,10‐seco 10(19)‐unsaturated ketone 22, the acetal 5‐acetate 21, and 5β,19‐epoxy derivative 23 (Scheme 9). Exceptionally, in the thermal Pb(OAc)4 oxidation of 9, the 5,10‐seco ketones 10, 11, and 22 were not formed, the only reaction being the stereoselective formation of the 5,10‐ethers with the β‐oriented epoxy bridge, i.e. the (10R)‐enol ether 20 and (5S,10R)‐acetal 5‐acetate 21 (Scheme 8). Possible mechanistic interpretations of the above transformations are discussed.