An expedited method has been developed for the enantioselective synthesis of highly functionalized steroid systems containing six contiguous stereogenic centers with high enantioselectivities (99% ee). The one-pot methodology comprises a cascade of organocatalytic Michael-Michael-aldol-Henry reactions of 7-nitrohept-3-en-2-one and 5-(1-methyl-2,5-dioxocyclopentyl)pent-2-enal. The structure and absolute configuration of the products were confirmed by X-ray analyses of appropriate products.