Preparation and temperature-dependent enantioselectivities of homochiral phenolic crown ethers having aryl chiral barriers: Thermodynamic parameters for enantioselective complexation with chiral amines

Koichiro Naemura*, Kazuyuki Nishioka, Kazuko Ogasahara, Yasushi Nishikawa, Keiji Hirose, Tobe Yoshito

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

42 Scopus citations

Abstract

Homochiral crown ether (S,S)-1 containing 1-naphthyl groups as chiral barriers together with the phenol moiety was prepared by using (S)-3 as a chiral subunit which was resolved in enantiomerically pure form by lipase- catalyzed enantioselective acylation of (±)-3. Homochiral phenolic crown ether (S,S)-2, containing phenyl groups as chiral barriers, was also prepared from (S)-5 which was derived from (S)-mandelic acid. The association constants for their complexes with chiral amines in CHCl3 were determined at various temperatures by the UV-visible spectroscopic method demonstrating that the crown ethers (S,S)-1 and (S,S)-2 displayed the large Δ(R)-(S)ΔG values of 6.2 and 6.4 kJ mol-1, respectively, towards the amine 21 at 15°C. Thermodynamic parameters for complex formation were also determined and a linear correlation between TΔ(R-S)ΔS and Δ(R-S)ΔH values was observed.

Original languageEnglish
Pages (from-to)563-574
Number of pages12
JournalTetrahedron Asymmetry
Volume9
Issue number4
DOIs
StatePublished - 27 Feb 1998

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