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
Date of Issue2017
School of Physical and Mathematical Sciences
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.
Journal of the American Chemical Society
© 2017 American Chemical Society (ACS). This is the author created version of a work that has been peer reviewed and accepted for publication by Journal of the American Chemical Society, American Chemical Society (ACS). It incorporates referee’s comments but changes resulting from the publishing process, such as copyediting, structural formatting, may not be reflected in this document. The published version is available at: [http://dx.doi.org/10.1021/jacs.7b05879].