Ionic hydrogenation of alkynes by HOTf and Cp(CO)3WH

Li Luan, Jeong Sup Song, R Morris Bullock

Research output: Contribution to journalArticle

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Abstract

Alkynes can be hydrogenated at room temperature by an ionic hydrogenation method using triflic acid (CF3SO3H) as the proton donor and a transition metal hydride (Cp(CO)3WH) as the hydride donor. Reaction of PhC≡CH with HOTf and Cp(CO)3WH gives ethylbenzene as the final product in high yield. Intermediates observed in this reaction are the vinyl triflate CH2=C(Ph)(OTf) and the geminal ditriflate Ph(CH3)C(OTf)2, which result from the addition of 1 or 2 equiv of HOTf to the C≡C triple bond of the alkyne. Hydrogenation of PhC≡CMe by HOTf and Cp(CO)3WH similarly produces propylbenzene as the ultimate product. Along with vinyl inflates, additional intermediates observed in this reaction were the cis and trans isomers of the β-methylstyrene complex [Cp(CO)3W-(η2-PhHC=CHCH3)] +[OTf]-. Hydrogenation of n-butylacetylene to n-hexane does occur upon reaction with HOTf/Cp(CO)3WH, but is very slow. In the absence of metal hydrides, 2-methyl-1-buten-3-yne reacts with HOTf to give the vinyl triflate CH2=CMeC(OTf)=CH2, but reaction with HOTf and Cp(CO)3WH gives Me2C=C(OTf)Me. The key characteristics required for the metal hydride used in these hydrogenations are the ability to donate hydride in the presence of strong acid, and the absence of rapid decomposition of the hydride through reaction with the strong acid. Cp(CO)3WH meets these requirements, but HSiEt3, while an effective hydride donor, is decomposed by HOTf on the time scale of these alkyne hydrogenation reactions.

Original languageEnglish
Pages (from-to)7170-7176
Number of pages7
JournalJournal of Organic Chemistry
Volume60
Issue number22
Publication statusPublished - 1995

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Alkynes
Carbon Monoxide
Hydrides
Hydrogenation
Metals
Acids
Isomers
Transition metals
Protons
Decomposition

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Ionic hydrogenation of alkynes by HOTf and Cp(CO)3WH. / Luan, Li; Song, Jeong Sup; Bullock, R Morris.

In: Journal of Organic Chemistry, Vol. 60, No. 22, 1995, p. 7170-7176.

Research output: Contribution to journalArticle

Luan, Li ; Song, Jeong Sup ; Bullock, R Morris. / Ionic hydrogenation of alkynes by HOTf and Cp(CO)3WH. In: Journal of Organic Chemistry. 1995 ; Vol. 60, No. 22. pp. 7170-7176.
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abstract = "Alkynes can be hydrogenated at room temperature by an ionic hydrogenation method using triflic acid (CF3SO3H) as the proton donor and a transition metal hydride (Cp(CO)3WH) as the hydride donor. Reaction of PhC≡CH with HOTf and Cp(CO)3WH gives ethylbenzene as the final product in high yield. Intermediates observed in this reaction are the vinyl triflate CH2=C(Ph)(OTf) and the geminal ditriflate Ph(CH3)C(OTf)2, which result from the addition of 1 or 2 equiv of HOTf to the C≡C triple bond of the alkyne. Hydrogenation of PhC≡CMe by HOTf and Cp(CO)3WH similarly produces propylbenzene as the ultimate product. Along with vinyl inflates, additional intermediates observed in this reaction were the cis and trans isomers of the β-methylstyrene complex [Cp(CO)3W-(η2-PhHC=CHCH3)] +[OTf]-. Hydrogenation of n-butylacetylene to n-hexane does occur upon reaction with HOTf/Cp(CO)3WH, but is very slow. In the absence of metal hydrides, 2-methyl-1-buten-3-yne reacts with HOTf to give the vinyl triflate CH2=CMeC(OTf)=CH2, but reaction with HOTf and Cp(CO)3WH gives Me2C=C(OTf)Me. The key characteristics required for the metal hydride used in these hydrogenations are the ability to donate hydride in the presence of strong acid, and the absence of rapid decomposition of the hydride through reaction with the strong acid. Cp(CO)3WH meets these requirements, but HSiEt3, while an effective hydride donor, is decomposed by HOTf on the time scale of these alkyne hydrogenation reactions.",
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AB - Alkynes can be hydrogenated at room temperature by an ionic hydrogenation method using triflic acid (CF3SO3H) as the proton donor and a transition metal hydride (Cp(CO)3WH) as the hydride donor. Reaction of PhC≡CH with HOTf and Cp(CO)3WH gives ethylbenzene as the final product in high yield. Intermediates observed in this reaction are the vinyl triflate CH2=C(Ph)(OTf) and the geminal ditriflate Ph(CH3)C(OTf)2, which result from the addition of 1 or 2 equiv of HOTf to the C≡C triple bond of the alkyne. Hydrogenation of PhC≡CMe by HOTf and Cp(CO)3WH similarly produces propylbenzene as the ultimate product. Along with vinyl inflates, additional intermediates observed in this reaction were the cis and trans isomers of the β-methylstyrene complex [Cp(CO)3W-(η2-PhHC=CHCH3)] +[OTf]-. Hydrogenation of n-butylacetylene to n-hexane does occur upon reaction with HOTf/Cp(CO)3WH, but is very slow. In the absence of metal hydrides, 2-methyl-1-buten-3-yne reacts with HOTf to give the vinyl triflate CH2=CMeC(OTf)=CH2, but reaction with HOTf and Cp(CO)3WH gives Me2C=C(OTf)Me. The key characteristics required for the metal hydride used in these hydrogenations are the ability to donate hydride in the presence of strong acid, and the absence of rapid decomposition of the hydride through reaction with the strong acid. Cp(CO)3WH meets these requirements, but HSiEt3, while an effective hydride donor, is decomposed by HOTf on the time scale of these alkyne hydrogenation reactions.

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