Enantioselective formation of a dynamic hydrogen-bonded assembly based on the chiral memory concept

Tsutomu Ishi-i, Mercedes Crego-Calama, Peter Timmerman, David N. Reinhoudt, Seiji Shinkai

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80 Citations (Scopus)


In this paper, we report the enantioselective formation of a dynamic noncovalent double rosette assembly 1a3·(CYA)6 composed of three 2-pyridylcalix[4]arene dimelamines (1a) and six butylcyanuric acid molecules (BuCYA). The six 2-pyridyl functionalities of the assembly interact stereoselectively with chiral dicarboxylic acids 3a-e via two-point hydrogen-bonding interactions. One of the two enantiomeric assemblies (P- or M-) 1a3·(CYA)6 is formed in excess as the result of the complexation of the chiral diacids, resulting in formation of optically active assemblies. The complexations with dibenzoly tartaric acids D-3a and L-3a (3 equivalent), respectively, leading to the formation of diastereomeric assemblies (P)-1a3· (BuCYA)6(D-3a)3 and (M)-1a3·(BuCYA)6·(L-3a)3 with 90% diastereomeric excess. The diastereomeric excess in (M)-1a3·(BuCYA)6·(L-3a)3 is "memorized" when L-3a is removed by precipitation with ethlylenediamine (EDA). The assembly (M)-1a3·(BuCYA)6 is still optically active (90% enantiomeric excess), although none of its individual components are chiral. (M)-1a3·(BuCYA)6 has a high kinetic stability toward racemization (Ea = 119 kJ mol-1, half-life of (M)-1a3·(BuCYA)6 is ca. 1 week at 20 °C).

Original languageEnglish
Pages (from-to)14631-14641
Number of pages11
JournalJournal of the American Chemical Society
Issue number49
Publication statusPublished - Dec 11 2002
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry


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