C-Aryl Glycosides via Tandem Intramolecular Benzyne−Furan Cycloadditions. Total Synthesis of Vineomycinone B₂ Methyl Ester

A triply convergent total synthesis of vineomycinone B2 methyl ester has been achieved by an approach with a longest linear sequence of 16 steps. The synthesis features the use of silicon tethers as disposable linkers to control the regiochemistry in two tandem Diels-Alder reactions of substituted benzynes and glycosyl furans to provide rapid access to the fully intact anthrarufin core of vineomycinone B2 methyl ester.