Bis-sulfonamide macrocycles as receptors for carboxylates

Abstract

This thesis is principally concerned with the synthesis of a range of bis-sulfonamide based macrocycles and their ability to bind carboxylates of amino acid derivatives.  Chapter I provides a general introduction to the field of supramolecular chemistry and discusses in detail carboxylate binding and its applications in chiral recognition of amino acids.  Chapter II describes the synthesis of acyclic bis-sulfonamide receptors.  Traditional NMR binding studies revealed their tendency to form complexes with a 1:2 host/guest stoichiometry.  The use of macrocyclic receptors proved to limit the formation of ternary complexes.  Cyclohexane based chiral macrocycles gave poor results in terms of carboxylate binding and showed no enantioselectivity with amino acids. Chapter III describes the synthesis of more flexible chiral macrocycles, built from valine.  Macrocyclisation reactions were carried out under anion templating conditions, which provided critical yield improvements.  Valine based macrocycles showed very strong affinity for the acetate anion and NMR titrations had to be conducted in MeCN-d₃/H₂O mixtures in order to obtain measurable binding constants.  Selectivity for acetate over other anions was found.  No enantioselectivity was shown in titrations with amino acids.  Chapter IV, finally, describes the synthesis of bis-sulfonamides macrocycles bearing additional polar groups.  In one particular case, moderate but general enantioselectivity was observed with N-protected amino acids displaying non-polar side chains.

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