Nickel(II)-Catalyzed Enantioselective α‑Vinylation of β‑Keto Amides/Esters with Hypervalent Iodine Salts

The enantioselective α-vinylation of β-keto amides/esters using hypervalent iodine salts has been accomplished via a chiral N,N′-dioxide–nickel­(II) complex promoted electrophilic addition and reductive elimination process. A wide range of vinyl-substituted all-carbon quaternary β-keto amides/esters were obtained in high yields and ee values (up to 99% yield and 99% ee). Moreover, the catalytic system has been applied to the enantioselective alkynylation/arylation of β-ketoamides with good results.