Hydrogen Bonding-Assisted Enhancement of the Reaction Rate and Selectivity in the Kinetic Resolution of d,l-1,2-Diols with Chiral Nucleophilic Catalysts

Kazuki Fujii, Koichi Mitsudo, Hiroki Mandai, Seiji Suga

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

An extremely efficient acylative kinetic resolution of d,l-1,2-diols in the presence of only 0.5mol% of binaphthyl-based chiral N,N-4-dimethylaminopyridine was developed (selectivity factor of up to 180). Several key experiments revealed that hydrogen bonding between the tert-alcohol unit(s) of the catalyst and the 1,2-diol unit of the substrate is critical for accelerating the rate of monoacylation and achieving high enantioselectivity. This catalytic system can be applied to a wide range of substrates involving racemic acyclic and cyclic 1,2-diols with high selectivity factors. The kinetic resolution of d,l-hydrobenzoin and trans-1,2-cyclohexanediol on a multigram scale (10g) also proceeded with high selectivity and under moderate reaction conditions: (i) very low catalyst loading (0.1mol%); (ii) an easily achievable low reaction temperature (0°C); (iii) high substrate concentration (1.0M); and (iv) short reaction time (30min).

Original languageEnglish
JournalAdvanced Synthesis and Catalysis
DOIs
Publication statusAccepted/In press - 2017

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Keywords

  • Acylation
  • Chiral nucleophilic catalyst
  • d,l-1,2-diols
  • Kinetic resolution
  • N,N-4-dimethylaminopyridine

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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