Novel Catalytic Reactions via Ruthena- or Rhodacyclic Intermediates with Atom-Efficiency

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  • ルテナサイクルおよびロダサイクル中間体の発生を鍵とする触媒的新合成反応
  • ルテナサイクル オヨビ ロダサイクル チュウカンタイ ノ ハッセイ オ カギ ト スル ショクバイテキ シン ゴウセイ ハンノウ

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Abstract

Novel catalytic reactions via ruthena- or rhodacyclic intermediates developed by our research group are reviewed. We initiate our study from (1) ruthenium-catalyzed [2 + 2] cycloaddition of alkynes with alkenes, followed by developing (2) intramolecular Pauson-Khand-type reaction of 1, 6-enynes, (3) hydroquinone synthesis, (4) codimerization of styrenes with ethylene . Another approach to construct novel functional monomers, such as cyclopentenones, pyranopyrandiones, and phenols, involves cleavage of carbon-carbon bonds in cyclobutenediones, cyclopropenones, and cyclobutenones. All reactions proceed with high atom-efficiency via ruthena- or rhodacyclicintermediates. In addition, rhodium-catalyzed [2 + 2 + 2] cocyclization of alkynes with isocyanates as well as novel ruthenium-catalyzed [2 + 2 + 1] cocyclization of alkynes, isocyanates, and carbon monoxide have been disclosed.

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