Catalytic cycloalumination in steroid chemistry: The introduction of a spirotetrahydrofuran or spirotetrahydroselenophene moiety into a 3′-methylene-(5α)-spirocholestane-3,1′-cyclobutane molecule

► For the first time catalytic cycloalumination in the steroid chemistry was accomplished. ► Efficient syntheses of novel steroidal cyclic organoaluminum compounds. ► A convenient one-pot method for spirofurane and spiroselenophene moiety formation on steroid. ► The structures of all novel compounds were confirmed by NMR measurements.