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 journalArticlepeer-review

17 Citations (Scopus)

Abstract

An extremely efficient acylative kinetic resolution of d,l-1,2-diols in the presence of only 0.5 mol% 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 (10 g) also proceeded with high selectivity and under moderate reaction conditions: (i) very low catalyst loading (0.1 mol%); (ii) an easily achievable low reaction temperature (0 °C); (iii) high substrate concentration (1.0 M); and (iv) short reaction time (30 min). (Figure presented.).

Original languageEnglish
Pages (from-to)2778-2788
Number of pages11
JournalAdvanced Synthesis and Catalysis
Volume359
Issue number16
DOIs
Publication statusPublished - Aug 17 2017

Keywords

  • N,N-4-dimethylaminopyridine
  • acylation
  • chiral nucleophilic catalyst
  • d,l-1,2-diols
  • kinetic resolution

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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