The synthesis of a chiral dinuclear [Cu(OAc)(L1)] complex (A) and its analogues Cu(OAc)(L1) (B), Cu(OAc)(L1)PPh (C), CuBr(L1)PPh (D), and Cu(OAc)(L2) (E) is described. The X-ray structure of A reveals a cuprophilic interaction (2.65 Å) and shows that L1 behaves as a monodentate ligand. The stereogenic centre in L1 aligns the NH group to form non-covalent interactions with the paddle-wheel acetate groups at variable distances (2.4-2.5 Å and 2.2-2.7 Å). Thermogravimetric analysis confirmed our hypothesis that two equivalents of L1 (B) or a combination of L1 and PPh (C) would disrupt the cuprophilic interaction. All complexes, except D, showed irreversible redox waves by cyclic voltammetry. Complexes C and E have lower oxidative peaks (at 10 V s) than complex A between +0.40 and +0.60 V. This highlights the influence of ligand(s) on the redox behaviour of Cu(II) complexes. The significance of this electrochemical behaviour was evident in the Chan-Lam (CL) coupling reaction, where 2.5 mol% of A successfully facilitated the formation of a C-N bond. This study showcased the structure, thermal stability, electrochemical properties and catalytic performance of a chiral dinuclear copper(II)-benzothiazolamine complex.
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http://dx.doi.org/10.1039/d3dt02994h | DOI Listing |
J Am Chem Soc
January 2025
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials, Dalian University of Technology, 2 Linggong Road, Dalian 116024, China.
Herein, we propose to synthesize stereoblock polythioethers through the chain shuttling enantioselective ring-opening polymerization (ROP) of thiiranes. The use of diastereoisomeric dinuclear Cr complexes with optimized steric hindrance allowed the production of polythioethers with both a head-to-tail content and isotacticity of >99%. In particular, the introduction of dithiols enabled the synthesis of stereoblock polythioethers via a chain shuttling process, thus producing sulfhydryl-telechelic polythioethers with tunable thermal properties.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Chemistry and Biomedicine Innovation Center (ChemBIC), State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, 210023, Nanjing, China Institution.
Drug resistance is a major cause of cancer recurrence and poor prognosis. The innovative design and synthesis of inhibitors to target drug-resistance-specific proteins is highly desirable. However, challenges remain in precisely adjusting their conformation and stereochemistry to adapt the chiral regions of target proteins.
View Article and Find Full Text PDFDalton Trans
November 2024
Área de Química Inorgánica, Departamento de Química, Universidad de La Laguna, C/Astrofísico Francisco Sánchez 3, 38071 La Laguna, Spain.
This research embarked on the study of a new binaphthyl phosphate scaffold of copper. There are two independent neutral complexes in the asymmetric unit: Cu1/Cu2 (I) and Cu3/Cu4 (II) from a similar structure to , with one arm formed by an intra-hydrogen bond between the water molecule bonded to the copper and the phosphine oxide (PO) moieties. Moreover, in the first complex two water and one ketone molecule complete the coordination sphere of the two-copper metals, instead, in the second one, one water and two ketone molecules.
View Article and Find Full Text PDFNat Commun
August 2024
College of Pharmaceutical Science & Collaborative Innovation Center of Yangtze River Delta Region Green Pharmaceuticals, Zhejiang University of Technology, Hangzhou, P. R. China.
N-oxides play a pivotal role in natural products and emerging drug design, while also serving as valuable ligand scaffolds in organometallic chemistry. Among heteroatom oxidations, the conversion of amines to N-oxides is a critical and challenging facet. We present here a highly enantioselective N-oxidation methodology for both cyclic and acyclic amines.
View Article and Find Full Text PDFDalton Trans
August 2024
Departament de Química Inorgànica i Orgànica, Secció de Química Inorgànica, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona, Spain.
The reaction of Ln(NO)·6HO (Ln = Nd, Sm, Eu, Tb, Dy, Tm and Yb) with the respective enantiopure ()-(-)-2-phenylbutyric or ()-(+)-2-phenylbutyric acid (/-2-HPhBut) and 4,7-diphenyl-1,10-phenanthroline (Bphen) allows the isolation of chiral dinuclear compounds of the formula [Ln(μ-/-2-PhBut)(/-2PhBut)(Bphen)] where Ln = Nd (R/S-Nd-a), Sm (R/S-Sm-a), Eu (R/S-Eu-a), Tb (R/S-Tb-a and R/S-Tb-b), Dy (R/S-Dy-a and R/S-Dy-b), Tm (R/S-Tm-b) and Yb (R/S-Yb-b). Single crystal X-ray diffraction was performed for compounds S-Eu-a and S-Tm-b. Powder crystal X-ray diffraction was performed for all complexes.
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