Catalytic Intramolecular Aminofluorination,Oxyfluorination, and Carbofluorination with a Stable and Versatile Hypervalent Fluoroiodine Reagent

Application of a fluoroiodine analogue of the Togni reagent was studied in fluorocyclization reactions. In the presence of a transition‐metal catalyst the applied fluoroiodine reagent can be used for aminofluorination, oxyfluorination, and carbofluorination reactions. The described procedure has a very broad synthetic scope for preparation of functionalized hetero‐ and isocyclic compounds having a tertiary fluorine substituent.     

Precise Synthesis of Ultra-High-Molecular-Weight Fluoropolymers Enabled by Chain-Transfer-Agent Differentiation under Visible-Light Irradiation

Ultra-high-molecular-weight (UHMW) polymers display outstanding properties and hold potential for wide applications. However, their precise synthesis remains challenging. Herein, we developed a novel reversible-deactivation radical polymerization based on the strong and selective fluorine–fluorine interaction, allowing chain-transfer agents to spontaneously differentiate into two groups that take charge of the chain growth and reversible deactivation of the growing chains, respectively. This method enables dramatically improved livingness of propagation, providing UHMW polymers with a surprisingly narrow molecular weight distribution (Đ≈1.1) from a variety of fluorinated (meth)acrylates and acrylamide at quantitative conversions under visible-light irradiation. In situ chain-end extensions from UHMW polymers facilitated the synthesis of well-defined block copolymers, revealing the excellent chain-end fidelity achieved by this method.