Highly active oligomeric Co(salen) catalysts for the asymmetric synthesis of α-aryloxy or α-alkoxy alcohols via kinetic resolution of terminal epoxides

Xunjin Zhu, Krishnan Venkatasubbaiah, Marcus Weck, Christopher W. Jones

Research output: Contribution to journalArticle

Abstract

A mixture of Co(salen) macrocycles, prepared via the ring expansion metathesis oligomerization of salen-functionalized cyclooctene monomers, among the most active soluble catalysts for the hydrolytic kinetic resolution (HKR) of terminal epoxides, is exploited as the catalyst in the ring-opening of epoxides using aliphatic alcohols or phenols as nucleophiles, leading to the direct synthesis of optically active α-aryloxy alcohols or α-alkoxy alcohols. The catalyst is compared to other dimeric, oligomeric and monomeric Co(salen) complexes including a pimelate-linked macrocyclic Co(salen) catalyst and a dimeric Co(salen) catalyst referred to as a bisalen. The catalysts that contain multiple Co(salen) units within a single molecular framework allow for substantial decreases in catalyst loading compared with the monomeric catalyst. The cyclooctene-based Co(salen) macrocycle catalyst allows for good activity and enantioselectivity in the ring-opening of terminal epoxides with phenols as nucleophiles, giving enhanced turnover frequencies relative to many literature catalysts. The cyclooctene-based Co(salen) macrocycle catalyst and the bisalen catalysts are shown to be the most active in the asymmetric ring-opening of (±)1,2-epoxyhexane with methanol, out-performing the other catalysts tested. The Co(salen) macrocycle catalyst is recycled 3 times in this reaction with some loss in activity but no noteworthy change in selectivity.

Original languageEnglish (US)
Pages (from-to)1-6
Number of pages6
JournalJournal of Molecular Catalysis A: Chemical
Volume329
Issue number1-2
DOIs
StatePublished - Aug 17 2010

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epoxy compounds
Epoxy Compounds
alcohols
Alcohols
catalysts
Catalysts
Kinetics
kinetics
synthesis
Nucleophiles
Phenols
nucleophiles
rings
disalicylaldehyde ethylenediamine
alkoxyl radical
phenols
Oligomerization
Enantioselectivity
metathesis
Methanol

Keywords

  • Cooperativity
  • Enantioselectivity
  • Epoxide
  • Phenol
  • Ring-opening

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry
  • Process Chemistry and Technology

Cite this

Highly active oligomeric Co(salen) catalysts for the asymmetric synthesis of α-aryloxy or α-alkoxy alcohols via kinetic resolution of terminal epoxides. / Zhu, Xunjin; Venkatasubbaiah, Krishnan; Weck, Marcus; Jones, Christopher W.

In: Journal of Molecular Catalysis A: Chemical, Vol. 329, No. 1-2, 17.08.2010, p. 1-6.

Research output: Contribution to journalArticle

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