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

Research output: Contribution to journalArticle

190 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)11917-11924
Number of pages8
JournalJournal of the American Chemical Society
Volume123
Issue number48
DOIs
Publication statusPublished - Dec 5 2001
Externally publishedYes

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Alkynes
Ruthenium
Aldehydes
Hydration
Metals
Metalloids
Hydrides
Hydrogen
Carbon
Acetylene
Deuterium
Carbon Monoxide
Protonation
Organometallics
Discrete Fourier transforms
Labeling
Byproducts
Experiments

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Ruthenium-catalyzed hydration of 1-alkynes to give aldehydes : Insight into anti-Markovnikov regiochemistry. / Tokunaga, Makoto; Suzuki, T.; Koga, N.; Fukushima, T.; Horiuchi, A.; Wakatsuki, Y.

In: Journal of the American Chemical Society, Vol. 123, No. 48, 05.12.2001, p. 11917-11924.

Research output: Contribution to journalArticle

Tokunaga, Makoto ; Suzuki, T. ; Koga, N. ; Fukushima, T. ; Horiuchi, A. ; Wakatsuki, Y. / Ruthenium-catalyzed hydration of 1-alkynes to give aldehydes : Insight into anti-Markovnikov regiochemistry. In: Journal of the American Chemical Society. 2001 ; Vol. 123, No. 48. pp. 11917-11924.
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