Novel lithocholaphanes: Syntheses, NMR, MS, and molecular modeling studies |
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Authors: | Arto Valkonen Elina Sievnen Satu Ikonen Nikolai V Lukashev Pavel A Donez Alexej D Averin Manu Lahtinen Erkki Kolehmainen |
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Institution: | aDepartment of Chemistry, University of Jyväskylä, P.O. Box 35, FIN-40014, University of Jyväskylä, Finland bDepartment of Chemistry, Lomonosov Moscow State University, Leninskie Gory, Moscow 119992, Russian Federation |
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Abstract: | Novel head-to-head lithocholaphanes 6 and 11 have been synthesized via precursors 1–5 and 7–10 with overall good yields, and characterized by 1H, 13C, and 15N NMR spectroscopy, ESI-TOF mass spectrometry, thermal analysis, and molecular modeling. In addition, the binding abilities of 6 and 11 towards alkali metal cations have been investigated via competitive complexation studies using equimolar mixtures of Li+, Na+, K+, and Rb+-cations, and cholaphanes 6 and 11. The formation of cation–cholaphane adducts was detected by ESI-TOF mass spectrometry. The trends in these comparative binding studies are nicely reproduced theoretically with PM3 energetically optimized structures of 6 and 11 and their interaction energies with alkali metal cations calculated by molecular mechanics. Cholaphane 11 possessing a peptoid type structural fragment, –(CH2CONHCH2CH2)2O–, as a coordination sphere, shows binding tendency towards lithium and sodium cations, whereas 6 possessing an ester type, –(CH2OCOCH2)2O–, moiety and a bigger cavity size than 11, shows merely a tendency towards bigger alkali metal cations, potassium and rubidium. |
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Keywords: | Lithocholaphane Synthesis NMR ESI-TOF MS Molecular modeling studies |
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