Enantioselective\nSynthesis of Chiral Acyclic Nitriles\nContaining α‑All-Carbon Quaternary Stereocenters via\nSynergistic Palladium and Phase-Transfer Catalysis

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