Ruthenium-catalyzed hydration of 1-alkynes to give aldehydes: Insight into anti-Markovnikov regiochemistry

Makoto Tokunaga, T. Suzuki, N. Koga, T. Fukushima, A. Horiuchi, Y. Wakatsuki

研究成果: Contribution to journalArticle査読

197 被引用数 (Scopus)

抄録

The mechanism of the selective conversion of 1-alkynes to aldehydes by hydration was investigated by isolating organic and organometallic byproducts, deuterium-labeling experiments, and DFT calculations. The D-labeled acetylenic hydrogen of 1-alkyne was found exclusively in the formyl group of the resulting aldehydes. After the reaction, the presence of metal-coordinated CO was confirmed. All of the experimental results strongly suggest the involvement of a metal-acyl intermediate with the original acetylenic hydrogen also bound to the metal center as a hydride, with the next step being release of aldehyde by reductive elimination. Theoretical analyses suggest that the first step of the catalytic cycle is not oxidative addition of acetylene C-H or tautomerization of η2-alkyne to a vinylidene complex, but rather protonation of the coordinated 1-alkyne at the substituted carbon to form a metal-vinyl intermediate. This cationic intermediate then isomerizes to Ru(IV)-hydride-vinylidene via α-hydride migration of the vinyl group to the metal center, followed by attack of the vinylidene α-carbon by OH- to give the metal-hydride-acyl intermediate.

本文言語英語
ページ(範囲)11917-11924
ページ数8
ジャーナルJournal of the American Chemical Society
123
48
DOI
出版ステータス出版済み - 12 5 2001
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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