Switchable Chemoselective Transfer Hydrogenations of Unsaturated Carbonyls Using Copper(I) N-Donor Thiolate Clusters

Meng Juan Zhang, Da Wei Tan, Hong Xi Li, David James Young, Hui Fang Wang, Hai Yan Li, Jian Ping Lang

Research output: Contribution to journalArticleResearchpeer-review

Abstract

Unsaturated alcohols and saturated carbonyls are important chemical, pharmaceutical, and biochemical intermediates. We herein report an efficient transfer hydrogenation protocol in which conversion of unsaturated carbonyl compounds to either unsaturated alcohols or saturated carbonyls was catalyzed by Cu(I) N-donor thiolate clusters along with changing hydrogen source (isopropanol or butanol) and base (NaOH or K2CO3). Mechanistic studies supported by DFT transition state modeling indicate that such a chemoselectivity can be explained by the relative concentrations of Cu(I) monohydride and protonated Cu(I) hydride complexes in each catalytic system.

Original languageEnglish
Pages (from-to)1204-1215
Number of pages12
JournalJournal of Organic Chemistry
Volume83
Issue number3
DOIs
Publication statusPublished - 2 Feb 2018
Externally publishedYes

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Hydrogenation
Copper
Alcohols
Carbonyl compounds
Butanols
2-Propanol
Discrete Fourier transforms
Hydrides
Hydrogen
Pharmaceutical Preparations
potassium carbonate

Cite this

Zhang, Meng Juan ; Tan, Da Wei ; Li, Hong Xi ; Young, David James ; Wang, Hui Fang ; Li, Hai Yan ; Lang, Jian Ping. / Switchable Chemoselective Transfer Hydrogenations of Unsaturated Carbonyls Using Copper(I) N-Donor Thiolate Clusters. In: Journal of Organic Chemistry. 2018 ; Vol. 83, No. 3. pp. 1204-1215.
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abstract = "Unsaturated alcohols and saturated carbonyls are important chemical, pharmaceutical, and biochemical intermediates. We herein report an efficient transfer hydrogenation protocol in which conversion of unsaturated carbonyl compounds to either unsaturated alcohols or saturated carbonyls was catalyzed by Cu(I) N-donor thiolate clusters along with changing hydrogen source (isopropanol or butanol) and base (NaOH or K2CO3). Mechanistic studies supported by DFT transition state modeling indicate that such a chemoselectivity can be explained by the relative concentrations of Cu(I) monohydride and protonated Cu(I) hydride complexes in each catalytic system.",
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Switchable Chemoselective Transfer Hydrogenations of Unsaturated Carbonyls Using Copper(I) N-Donor Thiolate Clusters. / Zhang, Meng Juan; Tan, Da Wei; Li, Hong Xi; Young, David James; Wang, Hui Fang; Li, Hai Yan; Lang, Jian Ping.

In: Journal of Organic Chemistry, Vol. 83, No. 3, 02.02.2018, p. 1204-1215.

Research output: Contribution to journalArticleResearchpeer-review

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AB - Unsaturated alcohols and saturated carbonyls are important chemical, pharmaceutical, and biochemical intermediates. We herein report an efficient transfer hydrogenation protocol in which conversion of unsaturated carbonyl compounds to either unsaturated alcohols or saturated carbonyls was catalyzed by Cu(I) N-donor thiolate clusters along with changing hydrogen source (isopropanol or butanol) and base (NaOH or K2CO3). Mechanistic studies supported by DFT transition state modeling indicate that such a chemoselectivity can be explained by the relative concentrations of Cu(I) monohydride and protonated Cu(I) hydride complexes in each catalytic system.

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