Reported herein is a novel reaction engineering protocol to enhance the efficiency of a transition metal-catalysed process by strategically preventing ligand degradation. Based on spectroscopic investigations, a decomposition pathway of a chiral phosphoramidite ligand during a Cu-catalysed reaction was identified. The involvement of the destructive process could be minimized under the modified reaction conditions that control the amount of nucleophilic alkoxide base, which is the origin of ligand decomposition. Overall, the strategy has been successfully applied to a new class of asymmetric conjugate addition reactions with bis[(pinacolato)boryl]methane, in which α,β-unsaturated enones are utilised as substrates.
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http://dx.doi.org/10.1039/d0sc06543a | DOI Listing |
J Chem Theory Comput
January 2025
Department of Chemistry and Biochemistry, The University of Texas at El Paso, El Paso, Texas 79968, United States.
In this work, we describe a computational tool designed to determine the local dielectric constants (ε) of charge-neutral heterogeneous systems by analyzing dipole moment fluctuations from molecular dynamics (MD) trajectories. Unlike conventional methods, our tool can calculate dielectric constants for dynamically evolving selections of molecules within a defined region of space, rather than for fixed sets of molecules. We validated our approach by computing the dielectric constants of TIP3P water nanospheres, achieving results consistent with literature values for bulk water.
View Article and Find Full Text PDFPolymers (Basel)
January 2025
Research Laboratory of Asymmetric Synthesis and Molecular Engineering of Materials for Organic Electronic (LR18ES19), Department of Physics, Faculty of Sciences of Monastir, University of Monastir, Avenue of Environment, Monastir 5019, Tunisia.
This paper explores a novel group of D-π-A configurations that has been specifically created for organic solar cell applications. In these material compounds, the phenothiazine, the furan, and two derivatives of the thienyl-fused IC group act as the donor, the π-conjugated spacer, and the end-group acceptors, respectively. We assess the impact of substituents by introducing bromine atoms at two potential substitution sites on each end-group acceptor (EG1 and EG2).
View Article and Find Full Text PDFOrg Lett
January 2025
Department of Chemistry, School of Science, China Pharmaceutical University, Nanjing 211198, People's Republic of China.
The development and enantioselective synthesis of two types of -symmetric spirobi[dihydrophenalene] structures is reported. The reaction proceeds via rhodium-catalyzed 2-fold asymmetric conjugate arylation of dienones followed by BF·OEt-promoted spirocyclization to give the enantiopure spiro products. Additive-dependent chemodivergent synthesis of 3,3'-diarylated 2,2',3,3'-tetrahydro-1,1'-spirobi[phenalene]-9,9'-diols (3,3'-Ar-SPHENOLs) and the corresponding spiro diary ethers from the same intermediate is achieved.
View Article and Find Full Text PDFMolecules
December 2024
Department of Chemistry, William & Mary, Williamsburg, VA 23185, USA.
The development of new antibiotics with unique mechanisms of action is paramount to combating the growing threat of antibiotic resistance. Recently, based on inspiration from natural products, an asymmetrical polyacetylene core structure was examined for its bioactivity and found to have differential specificity for different bacterial species based on the substituents around the conjugated alkyne. This research further probes the structural requirements for bioactivity through a systematic synthesis and investigation of new compounds with variable carbon chain length, alkynyl subunits, and alcohol substitution.
View Article and Find Full Text PDFNat Commun
January 2025
Key Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Materials (IAM), Nanjing Tech University (NanjingTech), Nanjing, China.
Fully π-conjugated polymers consisting of plane and rigid aromatic units present a fantastic optoelectronic property, a promising candidate for printed and flexible optoelectronic devices. However, obtaining high-performance conjugated polymers with an excellent intrinsically flexible and printable capacity is a great challenge due to their inherent coffee-ring effect and brittle properties. Here, we report an asymmetric substitution strategy to improve the printable and stretchable properties of deep-blue light-emitting conjugated polymers with a strong inter-aggregate capillary interaction for flexible printed polymer light-emitting diodes.
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