Helicoselective Synthesis of Indolohelicenoids via Organocatalytic Central‐to‐Helical Chirality Conversion

We report a helicoselective and convergent construction of indolohelicenoids with excellent efficiency and stereocontrol. This reaction proceeds through a chiral phosphoric acid (CPA) catalyzed enantioselective cycloaddition and eliminative aromatization sequence, which can be finely controlled by adjusting the reaction temperature. Mechanistic studies reveal that the chiral phosphoric acid cooperatively serves as both a bifunctional and Brønsted acid catalyst, enabling a one‐pot central‐to‐helical chirality conversion. Additionally, the optical properties of the synthesized indolohelicenoids were characterized to explore their potential applications in organic photoelectric materials.