Regio-, Site-, and Stereoselective Three-Component Aminofluorination of 1,3-Dienes via Cooperative Silver Salt and Copper Catalysis

The intermolecular fluorodifunctionalization of 1,3-dienes offers straightforward access to highly functionalized allylic fluorides but suffers from low selectivities and limited substrate scope. Herein, we report the development of a cooperative silver salt and copper catalysis platform that enables an intermolecular three-component 1,2-aminofluorination of 1,3-dienes with N-bromodialkylamines and AgF. This protocol exhibits a broad substrate scope for both alkyl- and aryl-1,3-dienes with diverse functionalities, furnishing the allylic fluorides bearing homoallylic tertiary alkylamine moieties with high regio-, site-, and stereoselectivities. Moreover, the reactions of E/Z-mixed 1,3-dienes are allowed for the preparation of single E-products. Further mechanistic studies reveal a reaction sequence involving aminium radical cation (ARC) generation, aziridinium formation, and nucleophilic fluorination and highlight the pivotal role of the cooperative silver and copper complexes that enable the proceeding of aminofluorination reactions with good efficiencies and high selectivities.