Studies of the Electronic Effects of Zinc Cluster Catalysts and Their Application to the Transesterification of β-Keto Esters

Kazushi Agura, Yukiko Hayashi, Mari Wada, Daiki Nakatake, Kazushi Mashima, Takashi Ohshima

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

The electronic effects of tetranuclear zinc cluster catalysts on transesterification were investigated by changing the carboxylate ligands in the clusters. High catalyst activity crucially depended on the balance between Lewis acidity and Brønsted basicity of the catalyst; this was consistent with the dual activation of both the electrophile and nucleophile by the cooperative zinc centers. In addition, tetranuclear zinc cluster catalysts achieved the transesterification of β-keto esters with unprecedented levels of broad substrate generality, in which a newly developed pentafluoropropionate-bridged zinc cluster and 4-dimethylaminopyridine additive greatly improved the reactivity of sterically congested α- and α,α-disubstituted β-keto esters. Lewis versus Brønsted: High catalyst activity of zinc clusters on transesterification crucially depend on a balance between Lewis acidity and Brønsted basicity of the catalyst. Zinc clusters, including a newly developed pentafluoropropionate-bridged zinc cluster, achieved the transesterification of β-keto esters with unprecedented levels of broad substrate generality (see figure).

Original languageEnglish
Pages (from-to)1548-1554
Number of pages7
JournalChemistry - An Asian Journal
Volume11
Issue number10
DOIs
Publication statusPublished - May 20 2016

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Transesterification
Zinc
Esters
Catalysts
Alkalinity
Acidity
Catalyst activity
Nucleophiles
Substrates
Chemical activation
Ligands

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Organic Chemistry

Cite this

Studies of the Electronic Effects of Zinc Cluster Catalysts and Their Application to the Transesterification of β-Keto Esters. / Agura, Kazushi; Hayashi, Yukiko; Wada, Mari; Nakatake, Daiki; Mashima, Kazushi; Ohshima, Takashi.

In: Chemistry - An Asian Journal, Vol. 11, No. 10, 20.05.2016, p. 1548-1554.

Research output: Contribution to journalArticle

Agura, Kazushi ; Hayashi, Yukiko ; Wada, Mari ; Nakatake, Daiki ; Mashima, Kazushi ; Ohshima, Takashi. / Studies of the Electronic Effects of Zinc Cluster Catalysts and Their Application to the Transesterification of β-Keto Esters. In: Chemistry - An Asian Journal. 2016 ; Vol. 11, No. 10. pp. 1548-1554.
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