Generation of Carbanions through Stibine–Metal and Bismuthine–Metal Exchange Reactions and Its Applications to Precision Synthesis of ω-End-Functionalized Polymers

Authors

  • Eiichi Kayahara,

    1. Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011 (Japan), Fax: (+81) 774-38-3067
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  • Hiroto Yamada,

    1. Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011 (Japan), Fax: (+81) 774-38-3067
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  • Prof. Dr. Shigeru Yamago

    Corresponding author
    1. Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011 (Japan), Fax: (+81) 774-38-3067
    2. CREST (Japan) Science and Technology Agency (Japan)
    • Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011 (Japan), Fax: (+81) 774-38-3067
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Abstract

Generation of carbanions from organostibines and organobismuthines through heteroatom–metal exchange reactions was examined from synthetic and mechanistic viewpoints. The exchange reaction proceeded spontaneously upon treatment with various organometallic reagents, such as alkyl lithiums, tetraalkyl zincates, and alkyl magnesium halides to afford the corresponding carbanions quantitatively. Due to the high reactivity of these heteroatom compounds, the exchange reactions took place exclusively even in the presence of various polar functional groups, which potentially react with organometallic species. The advantage of this method was exemplified by the end-group transformation of living polymers that bear these heteroatom species at the ω-polymer end, prepared by using organostibine and bismuthine-mediated living radical polymerizations. Various polymers that bear polar functional groups and acidic hydrogen—for example, poly(methyl methacrylate), poly(butyl acrylate), poly(N-isopropyl acrylamide), and poly(2-hydroxyethyl methacrylate)—could be used in the exchange reactions, and subsequent trapping with electrophiles afforded the corresponding polymers with controlled molecular weights, molecular weight distributions, and end-group functionalities. Competition experiments showed that organostibines and organobismuthines were among the most reactive heteroatom compounds towards organometallic reagents and that their high reactivity was responsible for the high chemoselectivity in the exchange reaction.

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