Full Control of the Regiospecific N -Functionalization of C -Functionalized Cyclam Bisaminal Derivatives and Application to the Synthesis of their TETA, TE2A, and CB-TE2A Analogues - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of Organic Chemistry Année : 2014

Full Control of the Regiospecific N -Functionalization of C -Functionalized Cyclam Bisaminal Derivatives and Application to the Synthesis of their TETA, TE2A, and CB-TE2A Analogues

Résumé

We describe an easy synthesis of original C-functionalized cyclam derivatives based on the efficient bisaminal template method. In the perspective of developing bifunctional chelating agents (BCAs), this new synthetic strategy offers the possibility of introducing various coupling functions on one carbon atom in the β-N position of the macrocycle, leaving the four nitrogen atoms available for the introduction of pendant coordinating arms. The methodology is based on a keystone C-functionalized oxo-cyclam bisaminal intermediate that is obtained by cyclization of a preorganized tetraamine using various methyl acrylate analogues. These compounds constitute valuable precursors for selective preparation of mono- and di-N-protected C-functionalized cyclams and C-functionalized cyclams, cross-bridged cyclams, and oxo-cyclam derivatives. This approach was successfully adapted to the synthesis of three BCAs with great interest especially for biomedical applications: TETA, TE2A, and CB-TE2A. The structures of different intermediates and Cu(II) complexes of C-functionalized cyclam derivatives were confirmed using single-crystal X-ray diffraction, while reactivity of the key intermediates was rationalized by the analysis of the electrostatic potentials calculated at the TPSSh/6-311G(d,p) level.
Fichier non déposé

Dates et versions

hal-01629496 , version 1 (06-11-2017)

Identifiants

Citer

Nathalie Le Bris, Nathalie Camus, Zakaria Halime, Hélène Bernard, Carlos Platas-Iglesias, et al.. Full Control of the Regiospecific N -Functionalization of C -Functionalized Cyclam Bisaminal Derivatives and Application to the Synthesis of their TETA, TE2A, and CB-TE2A Analogues. Journal of Organic Chemistry, 2014, 79 (5), pp.1885 - 1899. ⟨10.1021/jo4028566⟩. ⟨hal-01629496⟩
104 Consultations
0 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More