Kinetic resolution displaying zeroth order dependence on substrate consumption: Copper-catalyzed asymmetric alcoholysis of azlactones

Makoto Tokunaga, Junya Kiyosu, Yasushi Obora, Yasushi Tsuji

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28 Citations (Scopus)

Abstract

Kinetic resolution of 4-alkyl-2-aryl-5-oxo-4,5-dihydrooxazole-4-carboxylic acid esters (azlactones 1) were achieved by copper-DTBM-SEGPHOS catalyzed alcoholysis reaction with good selectivity (12 examples). Variation of ee of unreacted substrates 1 and products 2 with conversion was found to follow the theoretical line of zeroth-order kinetic resolution, for which the selectivity profiles and graphical analysis were presented for the first time. The efficiency of resolution in zeroth-order reaction is higher than first-order reaction. For example, the reaction with 1a afforded (S)-1a (99% ee) and (R)-2a (74% ee) at 57% conversion, where the krel values were calculated to be 6.7 as zeroth-order kinetic resolution and 37 as first-order kinetic resolution.

Original languageEnglish
Pages (from-to)4481-4486
Number of pages6
JournalJournal of the American Chemical Society
Volume128
Issue number13
DOIs
Publication statusPublished - Apr 5 2006
Externally publishedYes

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All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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