Side-reaction effects on dynamic kinetic resolution by enzyme-catalyzed irreversible acyl transfer

  • Yu Chi Cheng
  • , Shau Wei Tsai*
  • *Corresponding author for this work

Research output: Contribution to journalJournal Article peer-review

Abstract

An analytical solution for the dynamic kinetic resolution of enzyme-catalyzed irreversible acyl transfer was employed to study the side-reaction effects on the yield and optical purity of the desired enantiomeric product. A lipase-catalyzed enantioselective thiotransesterification between (R,S)-naproxen 2,2,2-trifluoroethyl thioester and 4-morpho-line ethanol with in situ racemization of (R)-thioester using trioctylamine as the racemization catalyst in isooctane was designed as a model system to compare the theoretical predictions. Under an initial water activity of 0.113, adding trioctylamine was found to have profound effects on the hydrolysis side-reactions, thus enhancing the chemoselectivity of the lipase to the alcohol in comparison with water. Theoretical analysis also indicated that the time-course yield and the enantiomeric excess for the desired enantiomer could be improved if the employed lipase had higher activity and enantioselectivity for the hydrolysis and esterification side-reactions, especially when the base had a similar racemization rate compared with the rate of the fast-reaction substrate.

Original languageEnglish
Pages (from-to)457-469
Number of pages13
JournalJournal of the Chinese Institute of Chemical Engineers
Volume34
Issue number4
StatePublished - 07 2003
Externally publishedYes

Keywords

  • (S)-Naproxen ester
  • Dynamic kinetic resolution
  • Esterification
  • Hydrolysis
  • Lipase
  • Thiotransesterification

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