Highly selective hydrolytic kinetic resolution of terminal epoxides catalyzed by chiral (salen)CoIII complexes. Practical synthesis of enantioenriched terminal epoxides and 1,2-diols

Scott E. Schaus, Bridget D. Brandes, Jay F. Larrow, Makoto Tokunaga, Karl B. Hansen, Alexandra E. Gould, Michael E. Furrow, Eric N. Jacobsen

Research output: Contribution to journalArticle

859 Citations (Scopus)

Abstract

The hydrolytic kinetic resolution (HKR) of terminal epoxides catalyzed by chiral (salen)CoIII complex 1·OAc affords both recovered unreacted epoxide and 1,2-diol product in highly enantioenriched form. As such, the HKR provides general access to useful, highly enantioenriched chiral building blocks that are otherwise difficult to access, from inexpensive racemic materials. The reaction has several appealing features from a practical standpoint, including the use of H2O as a reactant and low loadings (0.2-2.0 mol %) of a recyclable, commercially available catalyst. In addition, the HKR displays extraordinary scope, as a wide assortment of sterically and electronically varied epoxides can be resolved to ≥ 99% ee. The corresponding 1,2-diols were produced in good-to-high enantiomeric excess using 0.45 equiv of H2O. Useful and general protocols are provided for the isolation of highly enantioenriched epoxides and diols, as well as for catalyst recovery and recycling. Selectivity factors (krel) were determined for the HKR reactions by measuring the product ee at ca. 20% conversion. In nearly all cases, krel values for the HKR exceed 50, and in several cases are well in excess of 200.

Original languageEnglish
Pages (from-to)1307-1315
Number of pages9
JournalJournal of the American Chemical Society
Volume124
Issue number7
DOIs
Publication statusPublished - Feb 20 2002

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Epoxy Compounds
Kinetics
Catalysts
Catalyst selectivity
Recycling
disalicylaldehyde ethylenediamine
Recovery

All Science Journal Classification (ASJC) codes

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

Cite this

Highly selective hydrolytic kinetic resolution of terminal epoxides catalyzed by chiral (salen)CoIII complexes. Practical synthesis of enantioenriched terminal epoxides and 1,2-diols. / Schaus, Scott E.; Brandes, Bridget D.; Larrow, Jay F.; Tokunaga, Makoto; Hansen, Karl B.; Gould, Alexandra E.; Furrow, Michael E.; Jacobsen, Eric N.

In: Journal of the American Chemical Society, Vol. 124, No. 7, 20.02.2002, p. 1307-1315.

Research output: Contribution to journalArticle

Schaus, Scott E. ; Brandes, Bridget D. ; Larrow, Jay F. ; Tokunaga, Makoto ; Hansen, Karl B. ; Gould, Alexandra E. ; Furrow, Michael E. ; Jacobsen, Eric N. / Highly selective hydrolytic kinetic resolution of terminal epoxides catalyzed by chiral (salen)CoIII complexes. Practical synthesis of enantioenriched terminal epoxides and 1,2-diols. In: Journal of the American Chemical Society. 2002 ; Vol. 124, No. 7. pp. 1307-1315.
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abstract = "The hydrolytic kinetic resolution (HKR) of terminal epoxides catalyzed by chiral (salen)CoIII complex 1·OAc affords both recovered unreacted epoxide and 1,2-diol product in highly enantioenriched form. As such, the HKR provides general access to useful, highly enantioenriched chiral building blocks that are otherwise difficult to access, from inexpensive racemic materials. The reaction has several appealing features from a practical standpoint, including the use of H2O as a reactant and low loadings (0.2-2.0 mol {\%}) of a recyclable, commercially available catalyst. In addition, the HKR displays extraordinary scope, as a wide assortment of sterically and electronically varied epoxides can be resolved to ≥ 99{\%} ee. The corresponding 1,2-diols were produced in good-to-high enantiomeric excess using 0.45 equiv of H2O. Useful and general protocols are provided for the isolation of highly enantioenriched epoxides and diols, as well as for catalyst recovery and recycling. Selectivity factors (krel) were determined for the HKR reactions by measuring the product ee at ca. 20{\%} conversion. In nearly all cases, krel values for the HKR exceed 50, and in several cases are well in excess of 200.",
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