First Total Synthesis of (±)‐Rabelomycin

To hold the position for a labile hydroxyl group and to direct a regioselective deprotonation, the Si2Me5 group is introduced in the diene component 3, from which the antibiotic rac-rabelomycin (4) is accessible through cycloaddition and subsequent photooxygenation. This procedure emphasizes the usefulness of the pentamethylsilyllithium 2, readily prepared from disilane 1, for the synthesis of tertiary alcohols.