Bioinspired Network Analysis Enabled Divergent Syntheses and Structure Revision of Pentacyclic Cytochalasans

The bioinspired, divergent total syntheses of trichodermone and trichoderone A were accomplished from a common biogenetic precursor, aspochalasin Z. Key steps include transannular alkene cyclizations, a singlet oxygen ene reaction, and hydrogen atom transfer (HAT) cascade reactions. This approach validates the proposed biosynthetic pathway from a chemical perspective and paves the way for the synthesis and characterization of other cytochalasans.