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  • Title: Ruthenium-catalyzed hydration of 1-alkynes to give aldehydes: insight into anti-Markovnikov regiochemistry.
    Author: Tokunaga M, Suzuki T, Koga N, Fukushima T, Horiuchi A, Wakatsuki Y.
    Journal: J Am Chem Soc; 2001 Dec 05; 123(48):11917-24. PubMed ID: 11724598.
    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 [bond] H or tautomerization of eta(2)-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 alpha-hydride migration of the vinyl group to the metal center, followed by attack of the vinylidene alpha-carbon by OH(-) to give the metal-hydride-acyl intermediate.
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