Organocatalytic Regio- and Enantioselective [3+2]-Annulations of Ninhydrin-Derived Morita-Baylis-Hillman Carbonates with 3-Methyleneoxindoles

A type of Morita-Baylis-Hillman (MBH) carbonates has been developed from ninhydrin. These MBH carbonates have been successfully employed as 3C-synthons in the organocatalytic asymmetric [3 + 2]-annulations of the isatin-derived electron-deficient olefins, affording structurally diverse spirooxindoles in high yield with excellent stereoselectivity. In particular, the regioselectivity of MBH carbonates was controlled by the reaction partner, 3-methyleneoxindoles with carbonyl groups (R = ArCO), affording beta-selective products and 3-methyleneoxindoles with ester groups (R = CO2Me) furnishing gamma-selective products. The representative scale-up reactions and transformation of product were examined. The reaction mechanism was expounded by control experiments.