Electroreductive Radical Olefin Difunctionalization with Fluorinated Gases Enabled by Dosage Delivery from a...

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.