Dynamic ligand exchange of the lanthanide complex leading to structural and functional transformation: One-pot sequential catalytic asymmetric epoxidation-regioselective epoxide-opening process

Shin Ya Tosaki, Riichiro Tsuji, Takashi Ohshima, Masakatsu Shibasaki

研究成果: Contribution to journalArticle査読

89 被引用数 (Scopus)

抄録

The characteristic property of the lanthanide complex, which easily undergoes a dynamic ligand exchange and alters its structure and function in situ, is described. After the completion of the catalytic asymmetric epoxidation of various α,β-unsaturated amides 2 in the presence of the Sm-(S)-BINOL-Ph3-As=O (1:1:1) complex 1 (2-10 mol %), the addition of Me3SiN3 directly to the reaction mixture led to smooth epoxide-opening at room temperature, affording the corresponding anti-β-azido-α-hydroxyamide 4 in excellent overall yield (up to 99%) with complete regioselectivity and excellent enantiomeric excess (up to >99%). The key to the success of the sequential process was the in situ generation of the highly reactive samarium azide complex through dynamic ligand exchange. In situ IR spectroscopy and other experiments provided strong evidence that the samarium azide complex was generated. In addition, the relatively high Lewis basicity of the amide moiety had a key role in the high reactivity of both the epoxidation and the epoxide-opening reactions. Examinations of other nucleophiles such as sulfur or carbon nucleophiles as well as transformations of epoxide-opened products are also described.

本文言語英語
ページ(範囲)2147-2155
ページ数9
ジャーナルJournal of the American Chemical Society
127
7
DOI
出版ステータス出版済み - 2 23 2005
外部発表はい

All Science Journal Classification (ASJC) codes

  • 触媒
  • 化学 (全般)
  • 生化学
  • コロイド化学および表面化学

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