Total Synthesis of (+)-Superstolide A Mariola Tortosa Neal A. Yakelis William R. Roush 10.1021/jo801794s.s001 https://acs.figshare.com/articles/journal_contribution/Total_Synthesis_of_Superstolide_A/2891320 A convergent and highly stereocontrolled total synthesis of the cytotoxic macrolide (+)-superstolide A is described. Key features of this synthesis include the use of bimetallic linchpin <b>36b</b> for uniting the C(1)−C(15) (<b>43</b>) and the C(20)−C(27) (<b>38</b>) fragments of the natural product, a late-stage Suzuki macrocyclization of <b>49</b>, and a highly diastereoselective transannular Diels−Alder reaction of macrocyclic octaene <b>4</b>. In contrast, the intramolecular Diels−Alder reaction of pentaenal <b>5</b> provided the desired cycloadduct with lower stereoselectivity (6:1:1). 2008-12-19 00:00:00 diastereoselective intramolecular macrocyclic octaene 4. macrocyclization Suzuki Diel contrast synthesis bimetallic linchpin 36 b fragment stereocontrolled Superstolide transannular stereoselectivity Key features convergent cycloadduct cytotoxic macrolide Total Synthesis pentaenal 5 superstolide