Urea Derivatives of 1,4,7,10-Tetraazacyclododecane − Synthesis and Binding Properties

Abstract

Keywords: Azacrown ether / DNA binding / Macrocycles / Supramolecular chemistry / UreaThe reaction between 1,4,7,10-tetraazacyclododecane (cyclen) and partially protected derivatives and isocyanates gives macrocyclic ureas in good yields. Bridged biscyclens with aliphatic or aromatic spacers were obtained from the reaction between diisocyanates and partially protected cyclen. The substituted cyclen derivatives with one or two urea moieties coordinate zinc(II) and copper(II) ions to form stable mononuclear and dinuclear complexes. Potentiometric titration revealed that the urea substitution significantly changes the basicity of the remaining secondary amino groups of the macrocycle. In comparison with that of cyclen

Heteroligand copper(I) complexes of N-thiophosphorylated thioureas and phosphanes: Versatile structures and luminescence

“…The reaction of alkaline salts of the tetrakis-thiourea, containing a cyclam fragment cyclam(C(S)NHP(S)(OiPr) 2 ) 4 , with [Cu(PPh 3 ) 3 I] leads to the tetranuclear Cu(I) complex [{Cu(PPh 3 ) 2 } 4 Lig] (Chart 1) [5]. Furthermore, urea derivatives of cyclen and cyclam have, to the best of our knowledge, been reported so far in the literature by only two examples [5,6].…”

Functionalisation of Macroheterocycles with Preserving and Changing Their Sizes

“…oxygenated furan lactone-containing cembranoid [61] isolated from gorgonian. Treatment of α-siloxy aldehyde (89) with Li-HMDS proceeds with intramolecular cyclization to intermediate (90) that is accompanied with in situ lactonization with migration of the acyl group and leads to the sole diastereomer of furanocenbranoid (91). The removal of ethylene ketal protection and chemoselective acylation of secondary hydroxyl groups leads to macrocycle (92) that is semiproduct in synthesis of (88) (Scheme 22).…”

“…The resulting cyclen derivatives (38), (47) and (139) ions (Scheme 32). [91] Monoalkylation of trisubstituted cyclen (42b) and cyclam (43b) allows introducing such substituents as xylyl groups. Various bis-macrocycles coupled to each other ortho- (140a, 141a, 140b, 141b), meta-(140c, 141c, 140d, 141d) or para-(140e, 141e, 140f, 141f) Macroheterocycles (42b) and (43b) with a number of electrophilic compounds (115, 142a,b,d-h) (Scheme 33).…”

Investigation of carrier-mediated anion co-transport through organic membranes by use of competitive transport experiments

“…Literature procedures were used for synthesis of compounds 2 [15], 3 [16], 4 [17], 8 [18], 9-11 [19], 12 and 13 [20], 14 [21], 16 [22], and 24 [23].…”

“…The reaction with isocyanates is particularly efficient [35]. We have used the reaction of n-alkyl isocyanate 24 [23] with several azamacrocycles (25, 26, and 27) to transform them into hydrophobic cyclic ureas which might have anion binding abilities.…”