Mechanism of the chemo-bio catalyzed cascade synthesis of R-1-phenylethyl acetate over Pd/Al2O3, lipase, and Ru-catalysts

Alexey Kirilin, Päivi Mäki-Arvela*, Matthias Rupp, Esa Toukoniitty, Narendra Kumar, Krizstian Kordas, Leonid M. Kustov, Tapio Salmi, Dmitry Yu Murzin

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

6 Citations (Scopus)

Abstract

One-pot synthesis of R-1-phenylethyl acetate was investigated starting from acetophenone hydrogenation performed over Pd/Al2O3 and PdZn/Al2O3 catalysts followed by acylation of the intermediate secondary alcohol, R-1-phenylethanol, over an immobilized lipase. Furthermore, the performance of a third type of catalyst, Ru supported on hydroxyapatite (HAP) was evaluated for racemization of S-1-phenylethanol in one pot together with the two other catalysts. The main objectives of this work were to separate the effects of different catalysts and to reveal the reaction mechanism. For this purpose not only acetophenone, but also (R,S)-1- phenylethanol, S-1-phenylethanol, R-1-phenylethyl acetate, and styrene were used as reactants in combination with Pd/Al2O3, lipase and Ru/HAP as catalysts. The results revealed that the main side product, ethylbenzene, was formed in two different ways, via dehydration of (R,S)-1-phenylethanol to styrene, followed by its rapid hydrogenation to ethylbenzene, and via debenzylation of the desired product, R-1-phenylethyl acetate to ethylbenzene. The true one-pot synthesis, however, was demonstrated over Shvo's catalyst, but Ru/HAP was not sufficiently active in the racemization step. Ru/Al2O3 was a promising catalyst for racemization of S-1-phenylethanol and for dynamic kinetic resolution of (R,S)-1- phenylethanol, when using only small amounts of the acyl donor ethyl acetate. The challenge in racemization is that the activity of heterogeneous Ru catalysts was inhibited by esters.

Original languageEnglish
Pages (from-to)193-210
Number of pages18
JournalResearch on Chemical Intermediates
Volume36
Issue number2
DOIs
Publication statusPublished - Mar 2010
MoE publication typeA1 Journal article-refereed

Keywords

  • Acetophenone hydrogenation
  • Acylation
  • Chemo-bio cascade
  • Lipase
  • Pd
  • Ru

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