Solvent-Selective Reactions of Alkyl Iodide with Sodium Azide for Radical Generation and Azide Substitution and Their Application to One-Pot Synthesis of Chain-End-Functionalized Polymers

Journal of the American Chemical Society

5 years ago

Solvent-Selective Reactions of Alkyl Iodide with Sodium Azide for Radical Generation and Azide Substitution and Their Application to One-Pot Synthesis of Chain-End-Functionalized Polymers

Atsushi Goto, Chen-Gang Wang

Herein, a new reaction of an alkyl iodide (R–I) with an azide anion (N₃^–) to reversibly generate the corresponding alkyl radical (R^•) is reported. Via this new reaction, N₃^– was used as an efficient catalyst in living radical polymerization, yielding a well-defined polymer–iodide. A particularly interesting finding was the solvent selectivity of this reaction; namely, R–I and N₃^– generated R^• in nonpolar solvents, while the substitution product R–N₃ was generated in polar solvents. Exploiting this unique solvent selectivity, a one-pot synthesis of polymer–N₃ was attained. N₃^– was first used as a catalyst for living radical polymerization in a nonpolar solvent to produce a polymer–iodide and was subsequently used as a substitution agent in a polar solvent by simply adding the polar solvent, thereby transforming the polymer–iodide to polymer–N₃ in one pot. This one-pot synthesis was further applied to obtain N₃-chain-end-functionalized polymer brushes on the surface, uniquely controlling the N₃ coverage (number density). Using the chain-end N₃, the obtained linear and brush polymers were connected to functional molecules via an azide–alkyne click reaction. The attractive features of this system include facile operation, access to unique polymer designs, and no requirement for using excess NaN₃. In addition to N₃^–, thiocyanate (⁻SCN) and cyanate (⁻OCN) anions were also studied.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b05879

DOI: 10.1021/jacs.7b05879