A chiral tetraazamacrocycle 9 having four pendant-arms was synthesized by repeating ring opening of an Ns-aziridine with secondary amines, followed by macrocyclization. The structure of 9 has been determined by single crystal X-ray diffraction analysis and NMR studies. Sugar-hybrid molecules 12a-12f were synthesized based on the scaffold 9. NMR study showed that 12a-12f keep the similar conformation as 9 in solution.
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http://dx.doi.org/10.1021/ol9005954 | DOI Listing |
J Org Chem
April 2021
Department of Chemistry, The University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.
Tetraazamacrocycles, like cyclam , are well-studied polyamine ligands for metal ions that were first developed to model biological processes. Despite being studied for nearly 60 years, the development of chiral variants of has been limited. We report the synthesis of a chiral variant of , the tetraazamacrocycle .
View Article and Find Full Text PDFOrg Lett
March 2020
Université de Poitiers, IC2MP, UMR CNRS 7285, Equipe "Synthèse Organique", Groupe Glycochimie 4 rue Michel Brunet, 86073 Poitiers cedex 9, France.
A new family of chiral symmetric tetraazamacrocycles, coined ISAC for IminoSugar Aza-Crown, incorporating two iminosugars adopting a C conformation is disclosed. Multinuclear NMR experiments on the corresponding Cd complex show that the ISAC is a strong chelator in water and its tetramine cavity adopts a conformation similar to that of the parent Cd-cyclam complex. Similar behavior is observed with Cu in solution, with enhanced stability compared to the Cu-cyclam complex.
View Article and Find Full Text PDFInorg Chem
October 2019
The Hong Kong Polytechnic University Shenzhen Research Institute, Shenzhen 518000 , People's Republic of China.
One-step cyclization of a tetraazamacrocycle with 70% yield in a 25-g scale was performed. Its chiral DOTA derivatives, , has ∼93% of TSAP coordination isomer in its Eu(III) and Yb(III) complexes in aqueous solution. exhibits a high relaxivity, making it a promising and efficient MRI contrast agent.
View Article and Find Full Text PDFInorg Chem
September 2016
Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Hong Kong SAR, China.
High glum values of +0.30 (ΔJ = 1, 591 nm, in DMSO) and -0.23 (ΔJ = 1, 589 nm, in H2O) were recorded in our series of newly designed macrocyclic europium(III) complexes.
View Article and Find Full Text PDFChem Asian J
September 2013
Production Technology Laboratories, Kaken Pharmaceutical Co. Ltd. 301 Gensuke, Fujieda, Shizuoka 426-8646, Japan.
We previously reported that chiral Zn(2+) complexes that were designed to mimic the actions of class-I and class-II aldolases catalyzed the enantioselective aldol reactions of acetone and its analogues thereof with benzaldehyde derivatives. Herein, we report the synthesis of new chiral Zn(2+) complexes that contain Zn(2+)-tetraazacyclododecane (Zn(2+)-[12]aneN4) moieties and amino acids that contain aliphatic, aromatic, anionic, cationic, and dipeptide side chains. The chemical and optical yields of the aldol reaction were improved (up to 96 % ee) by using ZnL complexes of L-decanylglycyl-pendant [12]aneN4 (L-ZnL(7)), L-naphthylalanyl-pendant [12]aneN4 (L-ZnL(10)), L-biphenylalanyl-pendant [12]aneN4 (L-ZnL(11)), and L-phenylethylglycyl-pendant [12]aneN4 ligands (L-ZnL(12)).
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