Novel Route to 5-Position Vinyl Derivatives of Thiolactomycin: Olefination versus Deformylation.

Abstract Vinyl and diene derivatives of thiolactomycin have been prepared via Horner–Wadsworth–Emmons olefination from protected 5-formyl-3,5-dimethylthiotetronic acid. Several 4-position protecting groups and a variety of phosphonates were evaluated, with MOM protection and β-ketophosphonates yielding the highest ratio of the desired product to deformylated product.