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The neuromuscular blocking agents(NMBAs) are widely used in anesthesia as muscle relaxant.The steroid skeleton,decorated with two ammonium groups at proper positions,provides an excellent core for exploring potential NMBAs due to its rigidity.On the basis of the recent development on amino-steroidal neuromuscular blocking agents,we designed three new steroidal 3,16-bis-quaternary ammoniun salts.Starting from 16α-Br-5α-epaindrosterone,we got 6,7b and 7a after 5 steps(Scheme 1).