Synthesis of a C(4)–C(9) eleutheside template from d-glucal

Abstract d -Glucal is converted to epoxy allylic alcohol 4 using an eight-step sequence that features a stereoselective methyl Grignard addition to an iodo-hexenulose. Epoxide formation via intramolecular iodide displacement occurs subsequent to an unusual hemiacetal reduction protocol involving LiBH 4 in n -octanol. Alcohol 4 and the corresponding aldehyde ( Z )- 14 are potential C(4)–C(9) templates for eleutheside syntheses.