Construction of Vicinal Tertiary and All-Carbon Quaternary Stereocenters via Ir-Catalyzed Regio‑, Diastereo‑, and Enantioselective Allylic Alkylation and Applications in Sequential Pd Catalysis

Highly
congested vicinal stereocenters comprised of tertiary and
all-carbon quaternary centers were generated via Ir-catalyzed asymmetric
allylic alkylation of β-ketoesters. These catalytic reactions
proceed in excellent yields with a broad scope on either reaction
partner and with outstanding regio-, diastereo-, and enantiocontrol.
Implementation of a subsequent Pd-catalyzed alkylation affords dialkylated
products with pinpoint stereochemical control of both chiral centers.