Synthesis of Leiodolide A Macrolactone

• DOI: 10.1021/acs.orglett.5c00209
• Publication Date: 2025-03-06T14:13:08Z
• Authors: David R. Williams; Fese M. Okha; Sarah A. Ward

A convergent route toward the synthesis of leiodolide (1) is described. Our studies explored reactions indium chloride-induced transmetalation allylic stannane 32 for nucleophilic addition with nonracemic aldehyde 15. The stereoselective formation all-syn stereotriad was rationalized by an in situ isomerization to produce Z-allylindium reagent subsequent anti-Felkin addition. inversion C17 stereochemistry led effective π-allyl Stille cross coupling utilizing Z-alkenylstannane 11b. Horner-Wadsworth-Emmons reaction provides macrolactone 37 which exhibits discrepancies as compared reported NMR data purported A.