Stereocontrolled Total Synthesis of (−)-Callipeltoside A

[structure: see text] A highly stereocontrolled total synthesis of the cytotoxic macrolide (-)-callipeltoside A has been achieved in 23 steps (4.8% overall). Notable features include a novel asymmetric vinylogous aldol reaction to install the C13 stereocenter and (E)-trisubstituted alkene, an anti-selective aldol addition, a Sonogashira coupling, and, last, a Schmidt-type glycosylation to attach the sugar unit.