Synthesis of Leiodolide A Macrolactone

A convergent route toward the synthesis of leiodolide A () is described. Our studies explored reactions of the indium chloride-induced transmetalation of allylic stannane for nucleophilic addition with nonracemic aldehyde . The stereoselective formation of the all- stereotriad was rationalized by an isomerization to produce the -allylindium reagent for subsequent -Felkin addition. The inversion of C stereochemistry led to an effective π-allyl Stille cross coupling utilizing -alkenylstannane . The Horner-Wadsworth-Emmons reaction provides macrolactone which exhibits discrepancies as compared with reported NMR data for the purported leiodolide A.