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DOI: 10.1039/A904180J (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1999, 2557-2564

Structural and conformational studies of alcohol, diol and methyl ether derivatives of dibenzo-14-crown-4. Implications for ligand and tecton design

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Uriel Olsher, Gil Shoham, N. Kent Dalley, Jiang Weining, Elzbieta Luboch, Zong-Yuan Yu, John M. Knobeloch, Jong Chan Lee, Vladimir S. Talanov and Richard A. Bartsch

Abstract

Molecular structures are determined for six dibenzo-14-crown-4 derivatives that have one or two substituents on the central carbon(s) of the three-carbon bridge(s). The series of compounds includes three crown ether alcohols, one crown ether trans-diol, and two methoxy crown ether compounds. The crystal structures for these six crown ethers reveal that due to hydrogen-bonding and steric interactions, a hydroxy substituent is directed, at least partially, toward the crown ether cavity and an unusual intra- and intermolecular hydrogen bond network is formed between the hydroxy group protons and the ether oxygens of the crown ether ring. On the other hand, an ether group or a substituent with carbon as the first atom is oriented away from the polyether ring. The structure of sym-(methoxy)(methyl)dibenzo-14-crown-4 is markedly different from that of sym-(hydroxy)(methyl)dibenzo-14-crown-4 both in terms of the substituent orientation and very significant distortion from planarity of the four crown ether oxygens in the former. Support for an unusual conformation for sym-(methoxy)(methyl)dibenzo-14-crown-4 in solution is derived from 13C NMR measurements. Crown ether alcohols are hydrogen-bonding “tectons” that participate in strong, specific and directional intermolecular interactions.

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