Total Syntheses of Asparenyn, Gobicusin B, and PPAR‐agonist NNC 61‐4655 Through a FeCl3‐Assisted Electrophilic Fluorine‐Catalyzed 1,3‐Rearrangement of Allylic Alcohols

A FeCl3‐assisted electrophilic fluorine‐catalyzed 1,3‐rearrangement was developed, characterized by its mild catalytic system and broad substrate scope. The functional group tolerance of this approach was evaluated through a series of allylic alcohols readily prepared in situ from commercially available enones. Various nucleophiles, including water, amides, and Hantzsch esters, were utilized in the reaction. A plausible mechanism was proposed to elucidate the observed transformations, and the versatility of this methodology was demonstrated through the syntheses of asparenyn, gonicusin B, and the PPAR‐agonist NNC 61‐4655.