ブレンステッド塩基触媒による[1,2]-ホスファ-ブルック転位を利用した新たな分子変換反応

  • 近藤 梓
    東北大学大学院理学研究科附属巨大分子解析研究センター
  • 寺田 眞浩
    東北大学大学院理学研究科化学専攻

書誌事項

タイトル別名
  • Novel Transformations Utilizing [1,2]-Phospha-Brook Rearrangement Under Brønsted Base Catalysis
  • ブレンステッド エンキ ショクバイ ニ ヨル[1,2]-ホスファ-ブルック テンイ オ リヨウ シタ アラタ ナ ブンシ ヘンカン ハンノウ

この論文をさがす

抄録

<p>The [1,2]-phospha-Brook rearrangement involves the migration of the phosphorus moiety of the alkoxide of an α-hydroxyphosphonate from carbon to oxygen to generate an α-oxygenated carbanion. We have been focusing on the [1,2]-phospha-Brook rearrangement as a useful tool for the development of novel synthetic reactions under Brønsted base catalysis. For instance, we utilized the rearrangement for the catalytic generation of carbanions of less acidic compounds through the formal umpolung process from the corresponding carbonyl compounds. We have developed catalytic addition reactions of carbanions, such as enolates derived from less acidic amides and esters, α-oxygenated allyl anions that can serve as homoenolate equivalents and benzyl anions, as nucleophiles. We have also developed new efficient syntheses of functionalized allenes involving the generation of propargyl anions followed by regioselective protonation. The allenes were further applied to cycloisomerization to afford heterocyclic compounds, such as 2-aminofuran derivatives and indolizine derivatives. On the other hand, we utilized the [1,2]-phospha-Brook rearrangement for facilitating catalyst turnover in Brønsted base-mediated processes. Specifically, the [2,3]-Wittig rearrangement and the α-oxygenation of carbonyl compounds, which generally require a stoichiometric amount of Brønsted bases, have been successfully combined with the [1,2]-phospha-Brook rearrangement to proceed in a catalytic fashion.</p>

収録刊行物

被引用文献 (1)*注記

もっと見る

参考文献 (61)*注記

もっと見る

関連プロジェクト

もっと見る

詳細情報 詳細情報について

問題の指摘

ページトップへ