Ansafurantrienins, Unprecedented Ansatrienin Derivatives Formed via Photocatalytic Intramolecular [3 + 2] Oxidative Cycloaddition

Ansafurantrienins A–H, bearing a unique 5/6/8 dihydrofuran-fused benzo­[b]­azocine chromophore, were isolated from Streptomyces flaveolus. Their structures, especially in the dihydrofuran unit, were unambiguously established by spectroscopic analyses, molecular modeling, and TDDFT/ECD calculations. The ansafurantrienins were proposed to be generated via intramolecular [3 + 2] oxidative cycloaddition, which was achieved by photocatalytic reaction with UV light and oxygen and found to have solvent-dependent stereoselectivity. Ansafurantrienins showed significant antiproliferative effects against pancreatic cancer cells. The results led to a structural revision of strecacansamycins.