Pd‐Catalyzed Asymmetric Hydrogenolysis Rearrangement of Allylic Esters to Access Axially Chiral Olefins

Abstract The Pd‐catalyzed asymmetric hydrogenolysis rearrangement of allylic acetates using ( s ‐Bu) 3 BHK has been described, achieving the synthesis of axially chiral alkylidene cycloalkanes with excellent enantioselectivities (up to 99 % ee) and a wide substrate scope (30 examples of cyclohexanes and cyclobutanes). To the best of our knowledge, this is the first time to achieve synthesis of axially chiral olefins via asymmetric hydrogenolysis of allylic acetates. This methodology not only offers a novel synthetic pathway for non‐atropisomeric axially chiral structures but also highlights the potential of asymmetric hydrogenolysis as a powerful tool in synthetic organic chemistry.