Helicoselective Synthesis of Indolohelicenoids through Organocatalytic Central-to-Helical Chirality Conversion.

We report the helicoselective and convergent construction of indolohelicenoids with excellent efficiency and stereocontrol. This reaction proceeds through a chiral-phosphoric-acid-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 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.