Highly enantioselective organocatalytic oxidative kinetic resolution of secondary alcohols using chiral alkoxyamines as precatalysts: Catalyst structure, active species, and substrate scope

Keiichi Murakami, Yusuke Sasano, Masaki Tomizawa, Masatoshi Shibuya, Eunsang Kwon, Yoshiharu Iwabuchi

Research output: Contribution to journalArticlepeer-review

28 Citations (Scopus)

Abstract

The development and characterization of enantioselective organocatalytic oxidative kinetic resolution (OKR) of racemic secondary alcohols using chiral alkoxyamines as precatalysts are described. A number of chiral alkoxyamines have been synthesized, and their structure-enantioselectivity correlation study in OKR has led us to identify a promising precatalyst, namely, 7-benzyl-3-n-butyl-4-oxa-5-azahomoadamantane, which affords various chiral aliphatic secondary alcohols (ee up to >99%, krel up to 296). In a mechanistic study, chlorine-containing oxoammonium species were identified as the active species generated in situ from the alkoxyamine precatalyst, and it was revealed that the chlorine atom is crucial for high reactivity and enantioselectivity. The present OKR is the first successful example applicable to various unactivated aliphatic secondary alcohols, including heterocyclic alcohols with high enantioselectivity, the synthetic application of which is demonstrated by the synthesis of a bioactive compound.

Original languageEnglish
Pages (from-to)17591-17600
Number of pages10
JournalJournal of the American Chemical Society
Volume136
Issue number50
DOIs
Publication statusPublished - 2014 Dec 17

ASJC Scopus subject areas

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

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