Kinetic Resolution of the Nucleophile in Palladium-Catalyzed Allylic Alkylation

Significance

Kinetic resolution represents a powerful tool in asymmetric catalysis. Successful applications of this approach to palladium-catalyzed allylic substitutions have been reported; however, those studies predominantly focused on the resolution of allylic substrates, whereas limited attention has been devoted to resolution of nucleophiles. In this paper the authors report the ­kinetic resolution of 2,3-dihydro-2-substituted 4-quinolones using 1 as a chiral ligand. As a result, two adjacent chiral centers are present in the allylated product. Compound 2 was easily converted into 3, containing the core structure of Martinella alkaloids, which possess tachykinin receptor antagonistic activity. The protocol can be carried out on gram scale without loss of efficiency. However, the substrate scope is relatively narrow.