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Probing Persistent Intramolecular C−H···X (X = O, S, Br, Cl, and F) Bonding in Solution Using Benzyl Meldrum’s Acid Derivatives

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posted on 2009-02-06, 00:00 authored by Eric Fillion, Ashraf Wilsily, Dan Fishlock
Persistent intramolecular interactions between acidic C−H hydrogens and a variety of acceptors (X) (X = O, S, Br, Cl, and F) in solution were probed by 1H NMR experiments, using 5-benzyl Meldrum’s acid derivatives. To bring about formation of intramolecular C−H···X bonding, ortho-substituted benzyl Meldrum’s acids were designed, for which hydrogen bonding occurred through a six-membered ring. Introduction of substituents on the aromatic moiety and in the tether allowed variation of electronic and steric factors. The superior acidity of Meldrum’s acids impacted the ability of the C−H hydrogen to engage in nonclassical C−H···X bonds and drove the conformational properties of benzyl Meldrum’s acid, in combination with steric factors, namely A1,3-allylic strain. Further understanding of intramolecular C−H···X bonds was gained by characterization of benzyl Meldrum’s acids in the solid state, by X-ray analysis, and by the conformation correlated to the observations made in solution.

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