A [two-step/one week] synthesis of C-functionalized homocyclens and cyclams. Application to the preparation of conjugable BCAs without chelating properties alteration

Abstract : A versatile and efficient bisaminal template approach for the synthesis of cyclam and [13]aneN4 (homocyclen) bifunctional chelating agents (BCAs) bearing a hydroxyethyl function as a C-appended group is presented. The synthesis is rapid (two steps/one week) and does not require fastidious protection–deprotection steps or chromatographic purification. Another reactional route and alternative work-up give access to their oxo-cyclam and oxo-homocyclen analogues. The procedure consists of the cyclization of the preorganized tetraamine 1,4,8,11-tetraazaundecane, in its cis-butanedione-bisaminal form, with an α,β-unsaturated lactone to provide the tetracyclic oxo-intermediate whose bisaminal bridge can be easily removed and/or its amide function reduced under mild conditions. Furthermore, the synthetic route was successfully applied to the synthesis of teta and trita BCAs analogues starting from the linear tetraamine 1,4,7,10-tetraazadecane. Additionally, the appended alcohol functions of various cyclam and homocyclen based ligands were converted into their ethylamine functions following a very convenient procedure. Finally, preliminary analytical and complexation studies highlight that the supplementary hydroxyethyl C-appended chain has only a low impact on the acid–base behaviour and copper(II) or zinc(II) coordination properties of the macrocycle.
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RSC Advances, Royal Society of Chemistry, 2015, 5 (104), pp.85898 - 85910. 〈10.1039/c5ra17133d〉
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http://hal.univ-brest.fr/hal-01517785
Contributeur : Hélène Bernard <>
Soumis le : mercredi 3 mai 2017 - 16:09:54
Dernière modification le : jeudi 11 janvier 2018 - 06:17:06

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Nathalie Camus, Zakaria Halime, Nathalie Le Bris, Hélène Bernard, Maryline Beyler, et al.. A [two-step/one week] synthesis of C-functionalized homocyclens and cyclams. Application to the preparation of conjugable BCAs without chelating properties alteration. RSC Advances, Royal Society of Chemistry, 2015, 5 (104), pp.85898 - 85910. 〈10.1039/c5ra17133d〉. 〈hal-01517785〉

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