論文

査読有り
2018年3月27日

In Situ routes to catalytically active Ru(0) Species by reduction of readily available, air-stable precursors

Organometallics
  • Masafumi Hirano
  • ,
  • Hideyuki Kobayashi
  • ,
  • Takao Ueda
  • ,
  • Yuki Hiroi
  • ,
  • Ryota Abe
  • ,
  • Nobuyuki Komine
  • ,
  • Annie L. Colebatch
  • ,
  • Martin A. Bennett

37
7
開始ページ
1092
終了ページ
1102
記述言語
英語
掲載種別
研究論文(学術雑誌)
DOI
10.1021/acs.organomet.7b00882
出版者・発行元
American Chemical Society

Cross-dimerization of a conjugated diene with a substituted alkene catalyzed by in situ reduction of an air-stable Ru(II) catalyst precursor has been achieved. Reaction of 2,3-dimethylbutadiene with styrene is catalyzed by [Ru(acac)2(η4-1,5-COD)] (2a) (5 mol %) with BuLi (10 mol %) at 50 °C for 6 h in hexane, giving the cross-dimers in 99% yield ((E)-4,5-dimethyl-1-phenylhexa-1,4-diene (3a)/(E)-4,5-dimethyl-1-phenylhexa-2,4-diene (3b)/isomers = 84/9/7). Because neither 2a nor BuLi separately catalyzes the cross-dimerization and reduction of 2a with BuLi in the presence of naphthalene produces [Ru(η6-naphthalene)(η4-1,5-COD)] (1a), the active species in this catalysis is considered to be a Ru(0) compound. Interestingly, this in situ reduction method of Ru(II) using BuLi can be applied to the cross-dimerization using an ester such as methyl acrylate. Alternatively, an air-stable Ru(II) complex having a labile arene ligand such as [RuCl2(η6-anisole)]2 (5c) (5 mol %) with Na2CO3 (40 mol %) in the presence of 1,5-COD (20 mol %) at 100 °C for 6 h in 2-butanol also catalyzes the same cross-dimerization in 62% yield. These protocols provide facile methods for production of unsaturated linear compounds by the cross-dimerization using air-stable Ru(II) catalyst precursors.

リンク情報
DOI
https://doi.org/10.1021/acs.organomet.7b00882

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