Enantioselective Synthesis of Chiral Acyclic Nitriles Containing α‑All-Carbon Quaternary Stereocenters via Synergistic Palladium and Phase-Transfer Catalysis

Herein, we present a practical strategy for the asymmetric
synthesis
of chiral acyclic nitriles featuring α-all-carbon quaternary
stereocenters, utilizing synergistic palladium and phase-transfer
catalysis from allyl 2-cyanoacetates under mild conditions. This approach
offers an efficient and reliable method for the in situ generation
of tertiary α-cyano carbanions through intramolecular palladium-catalyzed
decarboxylative allylic alkylation. Additionally, it enables highly
enantioselective control of simple nitriles via ion-pairing interactions
with chiral phase-transfer catalysts. The synthetic utility of this
method is further demonstrated by its scalability to gram-scale synthesis
and its subsequent transformation into a variety of chiral functionalized
compounds containing acyclic all-carbon quaternary stereocenters.