辻‐Ｔｒｏｓｔ反応を用いた重縮合の開発と反応経路の制御による重縮合の新展開

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タイトル別名
  • Polycondensation Reaction Using the Tsuji-Trost Reaction, and a New Aspect of the Polycondensation via Controlled Reaction Pathways
  • ツジ Trost ハンノウ オ モチイタ ジュウシュクゴウ ノ カイハツ ト ハンノウ ケイロ ノ セイギョ ニ ヨル ジュウシュクゴウ ノ シンテンカイ

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The Tsuji-Trost reaction (TTR) has been one of the central topics in organic synthesis since its discovery. In spite of its spectacular success in organic synthesis, the typical reaction had not been utilized in polymer synthesis. Its uniqueness and effectiveness prompted us to develop the polymerization via TTR. Our examination of the reaction conditions revealed that 1, 4- bis (diphenylphosphino) butane (dppb) as a ligand and N, O-bis (trimethylsilyl) acetamide as a base were important. Degrees of polymerization in the polycondensation highly depend on the stoichiometric balance of the two monomers according to the Carothers-Flory equation. However, we found that the degrees of polymerization did not always depend on the stoichiometric balance of the monomers when the reaction pathways were controlled by catalysis. About sixty years later Carothers-Flory established the experimental and theoretical principles of homogeneous polycondensations, the highly controlled catalysis made a way to deviate the stoichiometric restriction in the polycondensation.

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