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Orthogonal C–B Bond Transformation as an Approach for Versatile Synthesis of End-Functionalized Polymers

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journal contribution
posted on 2022-05-04, 17:13 authored by Tomoaki Kanazawa, Tsuyoshi Nishikawa, Makoto Ouchi
Conventionally inaccessible end-functionalized vinyl polymers were synthesized via orthogonal side-chain replacement for terminal and repeating units of poly­(alkenyl boronate)­s. A terminal-defined polymer of isopropenyl boronic acid pinacol ester (IPBpin) was synthesized via RAFT polymerization, and subsequent cobalt (Co)-catalyzed end olefination afforded the polymer carrying the C­(sp2)–B bond at the terminal and the C­(sp3)–B bond in repeating units. Herein, the terminal C­(sp2)–B bond was selectively transformable via palladium (Pd)-catalyzed Suzuki-Miyaura cross coupling, and subsequent transformation of the repeating C­(sp3)–B unit gave the poly­(α-methyl vinyl alcohol) [poly­(MVA)] bearing various functional groups at the terminal. The boron-based stepwise polymer reaction thus overcame the synthetic difficulty of the end-functionalized poly­(MVA), which is ascribed to the poor polymerization ability of the corresponding acetate monomer, i.e., isopropenyl acetate.