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Generation of Cryptophanes in Water by Disulfide Bridge Formation

Abstract : Cryptophanes are receptors consisting of two bridging concave cyclotribenzylene (CTB) subunits. The formation of cryptophanes in basic aqueous solutions (0.1 M MOD; M = Li, Na, K, and Cs) by disulfide bridge formation has been investigated. Two original CTBs, 1H(6) and 2H(6), derived from cyclotriphenolene through the introduction of mercaptomethyl and mercapto substituents, respectively, were synthesized. Cryptophane formation by slow oxygenation of 1(6-) was observed only in the presence of Me4N+ as template, which yielded the diastereomeric forms in a ratio of around 82:18. By contrast, the rigid CTB 2H(6) yielded a cryptophane stereoselectively without a template. Interestingly, air oxidation of a 1:1 mixture of 1(6-) and 2(6-) in the presence of Me4N+ (0.5-1 equiv./1(6-)) in 0.1 m LiOD led to the exclusive formation of the cryptophane complex [(1.1)(6-)superset of+NMe4], (2.2)(6-) being formed only in very minor amounts. No mixed species were detected in the reaction mixtures. The stabilities of the diastereomers of the protonated cryptophanes were calculated in the gas phase by DFT at the omega B97XD 6-311G(d,p) level of theory.
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https://hal-univ-bourgogne.archives-ouvertes.fr/hal-01672003
Contributeur : Icmub - Université de Bourgogne <>
Soumis le : vendredi 22 décembre 2017 - 19:10:18
Dernière modification le : mardi 22 septembre 2020 - 18:18:02

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Frédérique Brégier, Oldřích Hudeček, Fanny Chaux, Marie-José Penouilh, Jean-Claude Chambron, et al.. Generation of Cryptophanes in Water by Disulfide Bridge Formation. European Journal of Organic Chemistry, Wiley-VCH Verlag, 2017, 2017 (26), pp.3795 - 3811. ⟨10.1002/ejoc.201700537⟩. ⟨hal-01672003⟩

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