Inverse-electron-demand Diels–Alder (IEDDA) reactions of electron-poor 2-pyrones as electrophilic dienes have been extensively studied in the past fifty years. These reactions provide an efficient access to bridged bicyclic lactones and their derivatives, such as densely functionalized 1,3-cyclohexadienes after CO2 extrusion and polysubstituted aromatic compounds through elimination. This reaction has been used for the synthesis of many biologically active natural products and drug candidates. In this review, the developments of these IEDDA reactions including non-catalytic, Lewis acid-catalyzed and organocatalytic IEDDA reactions, and their applications in total synthesis are discussed in detail. 相似文献
The complexity of polymer–protein interactions makes rational design of the best polymer architecture for any given biointerface extremely challenging, and the high throughput synthesis and screening of polymers has emerged as an attractive alternative. A porphyrin‐catalysed photoinduced electron/energy transfer–reversible addition‐fragmentation chain‐transfer (PET‐RAFT) polymerisation was adapted to enable high throughput synthesis of complex polymer architectures in dimethyl sulfoxide (DMSO) on low‐volume well plates in the presence of air. The polymerisation system shows remarkable oxygen tolerance, and excellent control of functional 3‐ and 4‐arm star polymers. We then apply this method to investigate the effect of polymer structure on protein binding, in this case to the lectin concanavalin A (ConA). Such an approach could be applied to screen the structure–activity relationships for any number of polymer–protein interactions. 相似文献
Highlights? Zebrafish provide a viable assay for the biological toxicity of 5-nitrofurans ? ALDH2 inhibitors prevent 5-nitrofuran toxicity in zebrafish and yeast ? Genetic dependence on ALDH2 for 5-nitrofuran toxicity in zebrafish and yeast systems ? 5-Nitrofurans bind to and are substrates of human ALDH2 相似文献
We report the first total synthesis of (?)‐17‐nor‐excelsinidine, a zwitterionic monoterpene indole alkaloid that displays an unusual N4?C16 connection. Inspired by the postulated biosynthesis, we explored an oxidative coupling approach from the geissoschizine framework to forge the key ammonium–acetate connection. Two strategies allowed us to achieve this goal, namely an intramolecular nucleophilic substitution on a 16‐chlorolactam with the N4 nitrogen atom or a direct I2‐mediated N4?C16 oxidative coupling from the enolate of geissoschizine. 相似文献
We describe here an asymmetric aldol reaction based on the principle of Memory of Chirality. From α-amino acids such as leucine and methionine, we have synthesized in two steps quaternary α-amino acid derivatives with high diastereoselectivity and enantioselectivity, using the chirality of the initial α-amino acid as the only chirality source. Furthermore, we were able to determine the relative and absolute configurations of the aldol products thanks to crystallographic structures and thus showed that the relative configuration depended on the aldehyde employed. We proposed a stereoselectivity explanation and obtained also quaternary β-hydroxy α-amino acids after acidic hydrolysis. 相似文献
In this critical review, it is shown how the introduction of chirality and the control of the absolute configurations of chiral elements in molecular magnets allow obtaining enantiopure chiral magnets (ECM), an archetype of multifunctional materials. This task has been recognised as a major challenge for both chemists and physicists of molecular magnetism. To reach this goal, the former have combined the rational approaches towards molecular-based magnets and of enantiopure metal-organic frameworks. They have used enantiopure stable radicals, ligands from the chiral pool, enantiopure coligands associated with achiral connectors or enantioselective self-assembly to successfully reach their synthetic targets. They were motivated by the will to obtain suitable systems for the experimental demonstration of the influence of enantiomeric purity on the physico-chemical properties. This influence can be found in the magnetic properties themselves but, most interestingly, in the coexistence and interaction between the properties arising from controlled non-centrosymmetry. Thus the combination of natural circular dichroism, second harmonic generation or ferroelectricity with long-range magnetic ordering can give birth to new properties like magneto-chiral dichroism, magnetisation induced second harmonic generation or multiferroicity. The two former synergetic effects have already been demonstrated in enantiopure chiral magnets. The third one remains a challenging target that can be reached by adapting strategies developed towards enantiopure molecular ferroelectrics (119 references). 相似文献
Nanoparticle chirality has attracted much attention recently, and the application of chiral nanoparticles to chiral technologies (see figure) is also of interest. This Minireview deals with advances in the preparation and characterization of chiral gold nanoparticles. Origins of the chiroptical properties and potential applications are discussed.
Numerical Algorithms - This paper presents some optimizations of a fast multipole symmetric Galerkin boundary element method code. Except general optimizations, the code is specially sped up for... 相似文献
Most genetic algorithms (GAs) used in the literature to solve control problems are time consuming and involve important storage memory requirements. In fact, the search in GAs is iteratively performed on a population of chromosomes (control parameters). As a result, the cost functional needs to be evaluated through solving the high fidelity model or by performing the experimental protocol for each chromosome and for many generations. To overcome this issue, a non-intrusive reduced real-coded genetic algorithm (RGA) for near real-time optimal control is designed. This algorithm uses precalculated parametrized solution snapshots stored in the POD (proper orthogonal decomposition) reduced form, to predict the solution snapshots for chromosomes over generations. The method used for this purpose is a economic reduced version of the Bi-CITSGM method (Bi-calibrated interpolation on the tangent space of the Grassmann manifold) designed specially for nonlinear parametrized solution snapshots interpolation. This approach is proposed in such a way to accelerate the usual Bi-CITSGM process by bringing this last to a significantly lower dimension. Thus, the whole optimization process by RGA can be performed in near real-time. The potential of RGA in terms of accuracy and central processing unit time is demonstrated on control problems of the flow past a cylinder and flow in a lid-driven cavity when the Reynolds number value varies. 相似文献
This contribution details an efficient and controlled photopolymerization regulated by far-red (λ=680 nm) and NIR (λ=780 and 850 nm) light in the presence of aluminium phthalocyanine and aluminium naphthalocyanine. Initiating radicals are generated by photosensitization of peroxides affording an effective strategy that provides controlled polymerization of a variety of monomers with excellent living characteristics. Critically, long wavelength irradiation provides penetration through thick barriers, affording unprecedented rates of controlled polymerization that can open new and exciting applications. Furthermore, a more optimized approach to performing solar syntheses is presented. By combining the narrow Q-bands of these photocatalysts with others possessing complementary absorptions, layered, independent polymerizations and organic transformations may be performed in parallel under a single broadband emission source, such as sunlight. 相似文献