Generation of Cryptophanes in Water by Disulfide Bridge Formation

Autor: Brégier , Frédérique, Hudeček , Oldřích, Chaux , Fanny, Penouilh , Marie-José, Chambron , Jean-Claude, Lhoták , Pavel, Aubert , Emmanuel, Espinosa , Enrique
Přispěvatelé: Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] (ICMUB), Université de Bourgogne (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Department of Organic Chemistry [Prague], University of Chemistry and Technology Prague (UCT Prague), Cristallographie, Résonance Magnétique et Modélisations (CRM2), Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Conseil Regional de Bourgogne (program PARI IME SMT8) 2010-9201AAO049S05301 Embassy of France in the Czech Republic Barrande PHC exchange program 31173WF A00807449, Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] ( ICMUB ), Université de Bourgogne ( UB ) -Centre National de la Recherche Scientifique ( CNRS ), Department of Organic Chemistry [University of Chemistry and Technology, Prague], University of Chemistry and Technology Prague ( UCT Prague ), Cristallographie, Résonance Magnétique et Modélisations ( CRM2 ), Université de Lorraine ( UL ) -Centre National de la Recherche Scientifique ( CNRS )
Jazyk: angličtina
Rok vydání: 2017
Předmět:
Zdroj: European Journal of Organic Chemistry
European Journal of Organic Chemistry, Wiley-VCH Verlag, 2017, 2017 (26), pp.3795-3811. ⟨10.1002/ejoc.201700537⟩
European Journal of Organic Chemistry, Wiley-VCH Verlag, 2017, 2017 (26), pp.3795-3811. 〈http://onlinelibrary.wiley.com/doi/10.1002/ejoc.201700537/abstract〉. 〈10.1002/ejoc.201700537〉
ISSN: 1434-193X
1099-0690
DOI: 10.1002/ejoc.201700537⟩
Popis: International audience; 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.
Databáze: OpenAIRE
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