Regio- and stereoselective syntheses of chiral α-quaternary (Z)-trisubstituted allylic amino acids via synergistic Pd/Cu catalysis.

Synergistic palladium/copper catalysis for asymmetric allylic alkylation of vinylethylene carbonates with aldimine esters has been developed for the synthesis of α-quaternary (Z)-trisubstituted allylic amino acids under mild conditions. This methodology features broad substrate compatibilities in yields of up to 87% and up to 94% ee. A facile scale-up and straightforward conversion to 1,2,3,5-tetrasubstituted pyrrole and 1,2,5,6-tetrahydropyridine bearing chiral quaternary carbon centers verifies the synthetic utility of this method.

Highly diastereo- and enantioselective synthesis of multisubstituted allylic amino acid derivatives by allylic alkylation of a chiral glycine-based nickel complex and vinylethylene carbonates.

The asymmetric synthesis of multisubstituted allylic amino acid derivatives was accomplished by the allylic alkylation of a chiral glycine-based nickel complex with vinylethylene carbonates. High enantioselectivities and diastereoselectivities were obtained under mild reaction conditions. The gram-scale synthesis was carried out with a good yield and high enantioselectivity, indicating that the method is a highly efficient route to chiral multisubstituted allylic amino acid derivatives.