Synthesis and Preliminary Structural and Binding Characterization of New Enantiopure Crown Ethers Containing an Alkyl Diarylphosphinate or a Proton-Ionizable Diarylphosphinic Acid Unit

New enantiopure crown ethers containing either an ethyl diarylphosphinate moiety [(S,S)‐4 to (S,S)‐7] or a proton‐ionizable diarylphosphinic acid unit [(S,S)‐8 to (S,S)‐11] have been synthesized. Electronic circular dichroism (ECD) studies on the complexation of these new enantiopure crown ethers wi...

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Veröffentlicht in:European journal of organic chemistry 2012-06, Vol.2012 (18), p.3396-3407
Hauptverfasser: Székely, György, Csordás, Barbara, Farkas, Viktor, Kupai, József, Pogány, Peter, Sánta, Zsuzsanna, Szakács, Zoltán, Tóth, Tünde, Hollósi, Miklós, Nyitrai, József, Huszthy, Péter
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Sprache:eng
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Zusammenfassung:New enantiopure crown ethers containing either an ethyl diarylphosphinate moiety [(S,S)‐4 to (S,S)‐7] or a proton‐ionizable diarylphosphinic acid unit [(S,S)‐8 to (S,S)‐11] have been synthesized. Electronic circular dichroism (ECD) studies on the complexation of these new enantiopure crown ethers with the enantiomers of α‐(1‐naphthyl)ethylammonium perchlorate (1‐NEA) and with α‐(2‐naphthyl)ethylammonium perchlorate (2‐NEA) were also carried out. These studies showed appreciable enantiomeric recognition with heterochiral [(S,S)‐crown ether plus either (R)‐1‐ or (R)‐2‐NEA] preference. Theoretical calculations found three significant intermolecular hydrogen bonds in the complexes of (S,S)‐9. Furthermore, preference for heterochiral complexes was also observed, in good agreement with ECD results. Complex formation constants were determined by NMR titration for four selected crown ether/NEA pairs. Enantiopure crown ethers containing either an ethyl phosphinate [(S,S)‐4 to (S,S)‐7] or a phosphinic acid moiety [(S,S)‐8 to (S,S)‐11] were synthesized and complexation with the enantiomers of 1‐ and 2‐NEA was studied. Calculations showed three important hydrogen bonds between (S,S)‐9 and each enantiomer of 1‐NEA and 2‐NEA. Appreciable enantiomeric recognition and heterochiral preference were found.
ISSN:1434-193X
1099-0690
DOI:10.1002/ejoc.201101769