Palladium‐Catalyzed Asymmetric [4+3]‐Cyclization Reaction of Fused 1‐Azadienes with Amino‐trimethylenemethanes: Highly Stereoselective Construction of Chiral Fused Azepines

Summary of main observation and conclusion A Pd‐catalyzed asymmetric aromative [4+3]‐cyclization reaction of amino‐trimethylenemethanes (TMM, 1,3‐dipoles) with fused 1‐azadienes has been developed. This method enables access to the synthetically importance and biologically active benzofuran fused azepines and indeno‐azepines in excellent efficiency and stereoselectivity (up to 95% yield, 99% ee, >19 : 1 dr).