Access to Chiral O,O‐Acetals Enabled by Palladium‐Catalyzed Asymmetric Addition of Oximes to Alkoxyallenes

Enantiomerically pure acyclic O,O‐acetal compounds (up to 97% ee) have been accessed through chemo‐, regio‐ and enantioselective palladium‐catalyzed addition of oximes to alkoxyallenes. DFT calculations support that a protonative hydropalladation pathway is favourable, in which the hydrogen bonding interaction between the amide group of the diphosphine ligand and the alkoxyallene is critical for the highly stereoselective formation of the dioxygenated stereogenic center.