Demonstrating a Folding Strategy Utilizing Phosphine‐Catalyzed Intramolecular Rauhut–Currier Reaction

A folding strategy of the diversity‐oriented synthesis (DOS) utilizing nucleophilic organophosphine‐promoted intramolecular Rauhut–Currier reaction is presented. Besides establishing a DOS variant, the strategy facilitates the rapid synthesis of highly substituted indanones and dibenzocycloheptanones under metal‐free and neutral conditions. Phosphines efficiently catalyze the transformation of various tethered bis‐enones, resulting in the formation of β ‐alkylated α ‐arylidene/allylidene indanones and dibenzocycloheptanones. These scaffolds are commonly found in numerous bioactive natural products and pharmaceutically relevant compounds. The broad applicability of the method across a wide range of substrates is demonstrated, and further enhances the skeletal and stereochemical diversity through several postsynthetic modifications.