Diels-Alder reaction of androsta-14,16-dien-17-yl acetates with nitroethylene: Product distribution and selected adduct transformations

► Addition of nitroethylene to dienyl acetates gives 3 products in a ratio 87:11:2. ► Reductive cleavage of nitroadduct with Ph3P gives 14β-cyanometyl derivative. ► Transfer hydrogenation was used for saturation Δ15-double bond. ► Solvolysis of nitroadduct gives mixture of 14,15-fused lactam and N-hydroxylactam.