Abstract: | Treated with the low‐valent titanium derived from TiCl4/Sm system, o‐nitrophenylazide could produce the intermediate 2 in situ, which reacted with benzoyl substituted ketene dithioacetals to afford 4‐aryl‐2‐methylthio‐3H‐1,5‐benzodiazepines in good yields under mild and neutral conditions. |