This paper reports the synthesis, characterization and electronic circular dichroism (ECD) spectroscopic studies of a new type of crown ethers and their achiral analogues containing a tetrahedral phosphorous centre. The synthetic routes to the two chiral phosphinate derivatives [(R,R)-10 and (R,R)-11] were similar, starting from the earlier reported ethyl bis(2-hydroxyphenyl)phosphinate and the unreported methyl bis(2-hydroxyphenyl)phosphinate, respectively. The enantiopure crown ether containing phosphinic acid unit (R,R)-14 was obtained by hydrolysis of the phosphinates (R,R)-10 and (R,R)-11, respectively. ECD spectroscopy was used for investigation of the chiroptical properties as well as complex formation ability of the novel enantiopure ligands. Owing to the presence of the aryl substituents the ECD spectra are rich in bands in the 1Bb, 1La and 1Lb regions (190-250 nm and 260-330 nm, respectively). In the case of (R,R)-14, a solvent dependent conformational behaviour was observed due to the strong dimer or aggregate forming ability of the POOH groups. This finding was supported by theoretical calculation of the monomer and the dimer forms. Phosphinates (R,R)-10 and (R,R)-11 form complexes with α-phenylethylammonium perchlorate (PEA) and α-(1-naphthyl)ethyl ammonium perchlorate (NEA) but do not discriminate between their enantiomers. All three chiral crown ethers bind strongly cations of ionic radii <∼1 Å.
Bibliographical noteFunding Information:
This work was supported by the Hungarian Scientific Research Fund (OTKA K62654 to P.H., PD71817 to V.F., PD71910 to T.T. and T49792, NI68466 to M.H.), GVOP-3.2.1-2004-04-0345/3,0 and by the Ministry of Education of Hungary (Postdoctoral Fellowship PAL 11/2003 to T.T.). The HPC Group computer facility, University of Szeged was used for several computations. The authors would like to thank Dr. Elemér Vass for helpful discussion.
ASJC Scopus subject areas
- Drug Discovery
- Organic Chemistry