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.
Keywords: Axial-to-central chirality transfer; Kinetic and DFT Studies; Unactivated allenes; ligand-assisted nucleopalladation; δ-carboxylation.
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