Disclosed herein is a dehydrosilylative difluoroamidation of α-Csp(3)-H of tetrahydroisoquinolines with α,α-difluoro-α-TMS-acetamides. The process, which occurs at ambient temperature in the absence of any transition metals, provides direct access to a broad range of α,α-difluoroacetamide-substituted tertiary amine derivatives in high yields. Moreover, the method was successfully applied in the Csp(3)-H-directed difluorophosphorylation and difluorocarboxylation under the same conditions.

The first example of decarboxylative difluoroacetamidation of α,β-unsaturated carboxylic acids by using difluoromethyl-substituted carbonyl compounds was disclosed. The procedure, which was mediated by low-cost and benign CuSO4, furnished a broad range of difluorinated alkenes in remarkable yields with only the E configuration in most of the cases. Moreover, the product could be smoothly transformed to the corresponding difluorofunctionalized ester and alcohol in high yields.

No abstract

This work concerns the Mg(OMe) promoted allylic isomerization of γ-hydroxy-α,β-alkenoic esters with TMEDA as an additive. The isomerization proceeded under mild conditions and afforded γ-keto esters in high yield (up to 96%) within 2 h. Both (Z)- and (E)-γ-hydroxy-α,β-alkenoic esters were tolerated under the reaction conditions. This transformation involves the in situ formation of a dienolate intermediate from the easily accessible γ-hydroxy-α,β-alkenoic ester. The in situ generated dienolate can react with benzaldehyde and undergo a practical, useful tandem allylic isomerization-Aldol reaction to afford more functionalized compounds.