Bi(OAc)<sub>3</sub>/Chiral Phosphoric Acid-Catalyzed Enantioselective 1,2- and Formal 1,4-Allylation Reaction of β,γ-Unsaturated α-Ketoesters
Xiang-Shuai Liu, Yao Li, Xin Li
Abstract
A highly efficient asymmetric 1,2-allylation reaction of β,γ-unsaturated α-ketoesters was realized by using a Bi(OAc)3/chiral phosphoric acid catalyst system under mild conditions. Meanwhile, using this combined strategy of enantioselective 1,2-allylation and subsequent anionic oxy-Cope rearrangement, the asymmetric formal 1,4-allylation reaction was achieved by a one-pot process. These reactions offer rapid access to an array of homoallylic tertiary alcohols and γ-allyl-α-ketoesters with good yields and excellent enantioselectivities. Density functional theory calculations were conducted to interpret the high enantioselectivity.
Topics & Concepts
Enantioselective synthesisPhosphoric acidChemistryCatalysisFormal synthesisReaction conditionsCombinatorial chemistryOrganic chemistryMedicinal chemistryAsymmetric Synthesis and CatalysisSynthetic Organic Chemistry MethodsChemical Synthesis and Analysis