Asymmetric Heck insertion/amination of nonconjugated cyclodienes proceeds to give 5‐aryl
cyclohexenylamines with good enantioselectivity and exclusive trans configurations. Primary
and secondary anilines, indoline, and benzylamines are suitable amines. The weakly
donating diphosphite Kelliphite forms a deep unsymmetrical pocket, which is essential for
stereoselective anti attack of amines.