Synthesis of 4‐aza‐5α‐sitostane (IX), and 4‐methyl‐4‐aza‐5α‐sitostane (XII) were accomplished through a set of reactions involving oxidative opening of ring A of α,β‐unsaturated ketone, ring closure, followed by catalytic hydrogenation and lithium aluminum hydride reduction, respectively. The antimicrobial activity for X and XII is reported.