Palladium‐Catalyzed, Regio‐/Stereo‐ and Enantiospecific <i>Anti</i>‐Carboxylation of Unactivated Internal Allenes

We report herein a directing group-controlled, palladium-catalyzed, regio-, stereo-, and enantiospecific anti-carboxylation of unactivated, internal allenes enabled via the synergistic interplay of a rationally designed bidentate directing group, palladium catalyst, and a multifunctional acetate ligand. The corresponding trans allyl ester was obtained in excellent yields with exclusive δ-regioselectivity and anti-carboxypalladation stereocontrol. The acetate ligand of the palladium catalyst controls the regio-, stereo- and enantioselectivity in the desired transformation. The potential of this concept has been demonstrated by the development of the chiral version of this transformation by using axial-to-central chirality transfer with good yields and enantioselectivities. Detailed investigations, including kinetic studies, order studies, and DFT studies, were performed to validate the ligand-assisted nucleopalladation process and the rationale behind the observed racemization of chiral allenes. The studies also indicated that the anti-carboxypalladation step was the rate-limiting as well as the stereo- and enantiodetermining step.