Transition-metal clusters as catalysts for chemoselective transesterification of alcohols in the presence of amines

Kazushi Mashima, Yukiko Hayashi, Kazushi Agura, Takashi Ohshima

Research output: Contribution to journalArticle

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Abstract

Acylation is one of the most abundant organic transformations of alcohols (esterification) and amines (amidation). Because of the greater nucleophilicity of the amino group compared to the hydroxyl group and the stability of amides compared to esters, N-acylation occurs predominantly in organic synthetic reactions. We reported that the μ-oxo-tetranuclear zinc cluster Zn 4(OCOCF3)6O efficiently catalyzes highly chemoselective acylation of hydroxyl groups in the presence of primary and secondary alkyl amino groups to afford the corresponding esters in high yields. Not only zinc carboxylate complexes but also various carboxylate complexes of first-row late transition metals, such as Mn, Fe, Co, and Cu, become catalysts for such the hydroxy group-selective acylation in the presence of amines. Among these carboxylate compounds, we found that the combination of an octanuclear cobalt carboxylate cluster [Co4(OCOR)6O]2 (R = CF3, CH3, and tBu) with nitrogen-containing ligands such as 2,2′-bipyridine show sufficient catalytic activity toward O-selective transesterification. Notably, an alkoxide-bridged dinuclear complex, Co2(OCOtBu)2(bpy) 22-OCH2-C6H4-4- CH3)2, was successfully isolated as a key intermediate that proceeds with Michaelis-Menten behavior through an ordered ternary complex mechanism similar to dinuclear metallo-enzymes, suggesting that the formation of alkoxides, followed by coordination of the ester, is responsible for the unique O-selective acylation.

Original languageEnglish
Pages (from-to)335-343
Number of pages9
JournalPure and Applied Chemistry
Volume86
Issue number3
DOIs
Publication statusPublished - Mar 20 2014

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Acylation
Transesterification
Amines
Transition metals
Alcohols
Catalysts
Esters
Hydroxyl Radical
Zinc
Esterification
Cobalt
Amides
Catalyst activity
Nitrogen
Enzymes
Ligands

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Transition-metal clusters as catalysts for chemoselective transesterification of alcohols in the presence of amines. / Mashima, Kazushi; Hayashi, Yukiko; Agura, Kazushi; Ohshima, Takashi.

In: Pure and Applied Chemistry, Vol. 86, No. 3, 20.03.2014, p. 335-343.

Research output: Contribution to journalArticle

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