ルテニウムポルフィリンの触媒する<i>N</i>-アシル環状アミン類の<i>N</i>-アシルアミノ酸への酸化的直接変換反応

• 伊藤 里奈

  名市大院薬

• 梅澤 直樹

  名市大院薬

• 樋口 恒彦

  名市大院薬

書誌事項

タイトル別名

• Unique Oxidation Reaction of Amides with Pyridine-<i>N</i>-oxide Catalyzed by Ruthenium Porphyrin – Direct Oxidative Conversion of <i>N</i>-Acyl-L-prolines to <i>N</i>-Acyl-L-glutamates

抄録

Oxidations of alkanes, alkenes, and aromatic rings with pyridine N-oxides are efficiently catalyzed by ruthenium porphyrins under mild conditions. We show here that the oxidation of N-acyl cyclic amines with Ru tetraarylporphyrin dichloride–2,6-substituted pyridine N-oxides directly gives N-acyl amino acids in modest to good yield via oxidative C–N bond cleavage. N-Acylazacycloalkanes were converted to N-acyl-ω-aminoalkanoic acids. This type of reaction is a novel one in which the C–N bond is cleaved selectively at the less substituted carbon. Notably, the proline residue in proline-containing peptides was selectively converted to glutamate. A large intramolecular kinetic isotope effect (k_H/k_D = 9.8) was observed in the oxidation of N-benzoyl[2,2,-d₂]pyrrolidine, indicating that the reaction should involve an α-hydrogen atom abstraction process as the rate-determining step.

収録刊行物

• 反応と合成の進歩シンポジウム 発表要旨概要

  反応と合成の進歩シンポジウム 発表要旨概要 30 (0), 186-187, 2004

  日本薬学会化学系薬学部会

キーワード

• ruthenium porphyrin
• ring-opening reaction
• oxidation
• pyridine <i>N</i>-oxide
• amino acid

詳細情報

• CRID: 1390282680611684096
• NII論文ID: 130006997459
• DOI: 10.14895/hannou.30.0.186.0
• データソース種別:
  • JaLC
  • CiNii Articles
• 抄録ライセンスフラグ: 使用不可