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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Published in:European journal of organic chemistry 2012-06, Vol.2012 (18), p.3396-3407
Main Authors: Székely, György, Csordás, Barbara, Farkas, Viktor, Kupai, József, Pogány, Peter, Sánta, Zsuzsanna, Szakács, Zoltán, Tóth, Tünde, Hollósi, Miklós, Nyitrai, József, Huszthy, Péter
Format: Article
Language:English
Subjects:
Chemistry
Circular dichroism
Condensed benzenic and aromatic compounds
Coordination compounds
Crown compounds
DFT calculations
Exact sciences and technology
Heterocyclic compounds
Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives
Host-guest systems
Inorganic chemistry and origins of life
Molecular recognition
NMR titration
Organic chemistry
Organometalloidal and organometallic compounds
P derivatives
Phosphorus
Preparations and properties
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Summary: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