Electroreductive Radical Olefin Difunctionalization with Fluorinated Gases Enabled by Dosage Delivery from a Metal–Organic Framework

Fluoroalkyl groups are crucial for tuning the pharmacokinetic properties of drug-like molecules, motivating the development of practical methods for their late-stage installation. Despite extensive progress, most contemporary fluoroalkylation strategies rely on impractical reagents or harsh reaction conditions, limiting their sustainability and scalability. Electrochemistry offers a compelling alternative by enabling controlled and tunable radical generation under mild conditions; however, electrochemical fluoroalkylation reactions, particularly reductive transformations, remain significantly underdeveloped. Herein, we report a general platform for electroreductive olefin difunctionalization that employs simple fluoroalkyl iodide gases (CF3I, CF3CF2I, and CF2HI) handled safely using the robust, inexpensive, recyclable, and redox-innocent metal-organic framework (MOF) Al-fum. Our method delivers streamlined access to fluoroalkylated products and enables electroreductive olefin difunctionalization for installing the medicinally important CF2H group. All reactions proceed with broad functional group tolerance (including for other alkyl halides) and are suitable for follow-on diversification. Together, our findings expand the scope of electroreductive fluoroalkylation chemistry and establish gas-MOF reagents as powerful tools to deliver fluoroalkyl iodide gases for electroorganic synthesis.