ChemInform Abstract: THE STEREOCHEMISTRY OF THIANE OXIDATION, PARTICIPATION OF NEIGHBORING GROUPS

Klein, Joseph; Stollar, H.

doi:10.1002/chin.197443132

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“…The selectivity is important, as isolation of the pure macrocycle would have been almost impossible due to the 16 different possible diastereoisomers that theoretically could have been formed by oxidation of the six sulfur atoms (Figure ). It has been shown that oxidation of thianes and biotin occurs in the equatorial position ( l -configuration), − and the hexasulfoxide is assigned as the l -isomer, having the oxygen atoms positioned exo on the bicyclic monomers. This places the sulfoxide oxygen atoms toward the portals of the macrocycle.…”

Section: Resultsmentioning

confidence: 99%

Entropy/Enthalpy Compensation in Anion Binding: Biotin[6]uril and Biotin-l-sulfoxide[6]uril Reveal Strong Solvent Dependency

et al. 2019

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Binding of anions using macrocyclic structures with a nonpolar interior using the CH···anion interaction as the recognition motif has gained popularity in the past few years, and such receptors often rely on a subtle interplay between enthalpic and entropic factors. For these types of receptors solvation of both the anion and the binding pocket of the macrocyclic host play important roles in the overall energetic picture of the binding event. Systematic chemical modifications of synthetic receptors that are able to bind anions in a variety of solvents is an important tool to gain understanding of the factors that determine the supramolecular chemistry of anions. Here we present the chiral macrocyclic structure biotin-l-sulfoxide[6]uril as a host molecule that binds anions in both water and in organic solvents. Biotin-l-sulfoxide[6]uril is prepared in a highly diastereoselective one-pot synthesis from the macrocycle biotin[6]uril. We compare the binding properties with that of biotin[6]uril, also studied in acetonitrile and in aqueous buffer at neutral pH. The biotin-l-sulfoxide[6]uril generally exhibits stronger recognition of anions in acetonitrile, but weaker binding in water as compared to the biotin[6]uril macrocycle. We have studied the binding events using a combination of NMR spectroscopy, isothermal titration calorimetry (ITC), and computational methods.

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Section: Resultsmentioning

confidence: 99%

Entropy/Enthalpy Compensation in Anion Binding: Biotin[6]uril and Biotin-l-sulfoxide[6]uril Reveal Strong Solvent Dependency

et al. 2019

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ChemInform Abstract: THE STEREOCHEMISTRY OF THIANE OXIDATION, PARTICIPATION OF NEIGHBORING GROUPS

Abstract: Thiane, die keine 4‐OH‐oder 4‐O‐Gruppe besitzen wie z.B. (I), werden durch Brom in Gegenwart von Wasser vorwiegend zum äquatorialen Thianoxid wie z.B. (II) oxidiert.

Cited by 1 publication

References 1 publication

Entropy/Enthalpy Compensation in Anion Binding: Biotin[6]uril and Biotin-l-sulfoxide[6]uril Reveal Strong Solvent Dependency

Entropy/Enthalpy Compensation in Anion Binding: Biotin[6]uril and Biotin-l-sulfoxide[6]uril Reveal Strong Solvent Dependency

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