Solvent-dependent self-discrimination of Bis(2-hydroxyphenyl)diamides

Akinobu Matsuzawa, Akihiro Nojiri, Naoya Kumagai, Masakatsu Shibasaki

Research output: Contribution to journalArticlepeer-review

25 Citations (Scopus)

Abstract

Solvent-dependent, self-dis-crimination of diamides is described. Mixing a solution of (A)-1a and (S)-1a, which are valine-derived, bis(2-hy-droxyphenyl) diamide-bearing, multiple hydrogen-bonding modules, in di-chloromethane immediately led to the formation of a thick suspension com-prising a 1: 1 heterochiral aggregate of la. The solubility of heterochiral la was substantially lower in halogenated solvents than in ethyl acetate. A perus-al of racemic crystal structures ob-tained from chloroform and ethyl ace-tate revealed a significant difference in the crystal-packing pattern, which is likely to be the basis for the pro-nounced difference in solubility. Specif-ic self-discrimination of la in an en-semble of eight structurally related molecules showcased the specific ag-gregation through the hydrogen-bond-ing network of the bis(2-hydroxyphe-nyl)diamide framework. The low solu-bility of heterochiral la in halogenated solvent was exploited to achieve high stereoselectivity in a catalytic asymmet-ric reaction by using a low enantiomer-ic excess sample of la.

Original languageEnglish
Pages (from-to)5036-5042
Number of pages7
JournalChemistry - A European Journal
Volume16
Issue number17
DOIs
Publication statusPublished - 2010 May 3
Externally publishedYes

Keywords

  • Aggregation
  • Asymmet-ric catalysis
  • Chiral resolution
  • Molecular recognition
  • Self-assembly
  • Stacking interactions

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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