Metal-directed switching of enantioselectivity in the Mukaiyama-Michael reaction of silyl enol ethers to α,β-unsaturated 2-acyl imidazoles using the same chiral indapybox ligand has been reported. The utility of this approach has been portrayed in the synthesis of both enantiomers of optically active δ-keto acid and ester as well as 3,4-dihydropyran-2-one. Moreover, enantioswitching in the construction of the tertiary stereocenter adjacent to a gem-dimethyl group has been achieved.

Chiral bifunctional urea-catalyzed asymmetric direct hetero-Diels–Alder reaction between alkylidene azlactone-derived dienes and trifluoromethyl aryl ketones is reported for the first time. The direct hetero-Diels–Alder reaction followed by ring opening results in densely functionalized α,β-unsaturated δ-lactones featuring a CF3-substituted quaternary stereocenter in high yields with excellent enantioselectivities. The method is compatible over a range of substrates. Moreover, the reaction is scaled up and the α,β-unsaturated δ-lactones were converted to amino acid derivatives decorated with trifluoromethylated carbinol functionality.

A highly diastereo- and enantioselective vinylogous Mukaiyama-Michael reaction of silyloxyfurans with α,β-unsaturated 2-acyl imidazoles catalyzed by either chiral Sc(iii) or Er(iii) complexes of a pybox ligand has been reported. The enantioenriched γ-butenolides formed in the reaction were further transformed into highly functionalized γ-lactones found as important structural frameworks in a wide range of biologically active natural products.

An efficient method for the regioselective synthesis of uracil-, coumarin-and quinolone-fused benzosultams and benzosultones is reported. The method offers a synthetic route to highly functionalized sultam and sultone derivatives in 75-95% yield under mild conditions. Density functional theory studies have been used to explain the regioselectivity in the synthesis of the coumarin-and quinolone-fused sultams and sultones.