Ir-Catalyzed Asymmetric Allylic Alkylation of Dialkyl Malo-nates Enabling the Construction of Enantioenriched All-Carbon Quaternary Centers

ABSTRACT: An enantioselective iridium-catalyzed allylic alkylation of malonates with trisubstituted allylic electro-philes to form all-carbon quaternary stereocenters is reported. This cross-coupling reaction features unprecedented reactivity at ambient temperature, particularly for challenging fully alkyl-substituted allylic electrophiles, and ena-bles the preparation of a wide range of enantioenriched products in up to 93% yield and 97% ee. The products of this transformation can be readily converted to a number of valuable building blocks including vicinal quaternary stereodiads and β-quaternary acids. This method was also used to prepare an enantioenriched intermediate facilitat-ing the asymmetric formal synthesis of the sporochnol family of natural products.