Publication
A new general three-stage strategy to access polycyclic ring systems bearing all-carbon quaternary centers with high enantioselectivity is reported. The required starting materials were readily accessed in racemic form through the alpha-alkynylation of ketoesters with EBX (EthynylBenziodoXolone) hypervalent iodine reagents. A Pd-catalyzed asymmetric decarboxylation allylation was then achieved in high yields and enantioselectivities with Trosts biphosphine ligands. Finally, transition-metal catalyzed cyclization of the obtained chiral enynes gave access to fused and spiro polycyclic ring systems constituting the core of many bioactive natural products.