Asymmetric Remote Addition Reactions of Heterocycle‐Based Dearomative Dienamine or Trienamine Species to 1‐Azadienes: Application to Construct Chiral Azocanes and Azecanes

The dearomative dienamines between a few five‐membered heteroaryl aldehydes and chiral secondary amine catalysts underwent highly regio‐, chemo‐ and stereoselective Michael additions to 1‐azadienes derived from 2‐methylenebenzofuran‐3(2H)‐ones or 2‐methylenebenzo[b]thiophen‐3(2H)‐ones. The very remote ε‐regioselective Michael‐type additions could be similarly realized by employing the analogous dearomative trienamine species from β‐indolyl unsaturated aldehydes. The resulting multifunctional products enabled the efficient construction of enantioenriched chiral azocane or even azecane frameworks with high molecular complexity.