Iron‐<i>N</i>,<i>N</i>,<i>N</i>’,<i>N</i>’‐Tetramethylethylenediamine‐Catalyzed Selective Substitution of Functionalized Diene and Triene Monoepoxides with Aliphatic Grignard Reagents

Abstract

When γ,δ‐epoxy‐α,β‐unsaturated esters were treated with 3 equiv. of aliphatic Grignard reagents in the presence of 10 and 20 mol% of FeCl<sub>2</sub> and <i>N</i>,<i>N</i>,<i>N</i>’,<i>N</i>’‐tetramethylethylenediamine (TMEDA), regio‐ and stereoselective substitution of the epoxide moiety with the aliphatic Grignard reagent occurred to give exclusively δ‐hydroxy‐γ‐alkyl‐α,β‐unsaturated esters in high yields. In addition, γ,δ‐epoxy‐α,β,ε,ζ‐unsaturated esters and amides afford the corresponding δ‐hydroxy‐γ‐alkyl‐α,β,ε,ζ‐unsaturated esters and amides, respectively, with high selectivity.