A perfluoroalkylsulfonyl fluoride-mediated abnormal Beckmann rearrangement is reported which transforms steroid 17-oximes to the corresponding alkene nitriles regioselectively in good yields. This reaction is rapid (completes in 25 min), mild (proceeds at room temperature) and, most importantly, tolerates various acid-labile functional groups, such as methoxymethyl (MOM), ketal, and methyl enol ether, providing access to molecules that would be difficult to synthesize using existing methods.A perfluoroalkylsulfonyl fluoride-mediated abnormal Beckmann rearrangement is reported which transforms steroid 17-oximes to the corresponding alkene nitriles regioselectively in good yields. This reaction is rapid (completes in 25 min), mild (proceeds at room temperature) and, most importantly, tolerates various acid-labile functional groups, such as methoxymethyl (MOM), ketal, and methyl enol ether, providing access to molecules that would be difficult to synthesize using existing methods.

The first chemical synthesis of glaucogenin D, a 13,14:14,15-disecopregnane steroid with potential antiviral activity, has been accomplished in 12 steps from a hirundigenin-type intermediate. The present route would also be amenable to the synthesis of natural and unnatural glaucogenin derivatives for SAR studies.