Total Synthesis of Myceliothermophins C,D, and E

The total synthesis of cytotoxic polyketides myceliothermophins E ( 1 ), C ( 2 ), and D ( 3 ) through a cascade‐based cyclization to form the trans‐fused decalin system is described. The convergent synthesis delivered all three natural products through late‐stage divergence and facilitated unambiguous C21 structural assignments for 2 and 3 through X‐ray crystallographic analysis, which revealed an interesting dimeric structure between its enantiomeric forms.