手性配体在钯催化不对称碳氢键活化反应中的应用

目前,手性配体辅助钯催化的区域和对映选择性碳氢键活化是过渡金属催化的前沿领域.在过去的十年中,它作为一种越来越重要的合成工具,用于合成含有各种不对称元素(中心手性、轴手性和平面手性)的手性分子,也是快速构建各种碳碳键和碳杂原子键的最有效方法之一.本文介绍了一些典型手性配体在钯催化不对称sp²和sp³碳氢键活化/官能团化反应中的应用,如单齿配体亚磷酰胺、手性磷酸(CPAs)和双功能氮端单保护的氨基酸(MPAAs)配体;探讨了这些手性配体辅助催化反应的创新性和特点,在理清这一研究领域发展脉络的同时,展望了未来研究工作的方向.此外,本文还介绍了这一不对称合成策略在天然产物、药物分子全合成中的应用.     

Short Radiative Lifetime and Non-Triplet Sensitization in Near-Infrared-Luminescent Yb(III) Complex with Tripodal Schiff Base

We prepared Ln(III) (Ln=Eu, Gd, and Yb) complexes with a tripodal Schiff base, tris[2-(5-methylsalicylideneimino)ethyl]amine (H₃L) and studied their photophysical properties. Upon ligand excitation, YbL showed Yb(III)-centered luminescence in the near-infrared region. While the overall quantum yield (0.60(1)%) of YbL in acetonitrile was moderate among the reported values for Yb(III) complexes, its radiative lifetime (0.33(2) ms) was significantly shorter than those reported previously. We propose that the ligand-to-metal charge-transfer (LMCT) state mediated the sensitization in YbL. The emission and excitation spectra of EuL indicated the participation of the LMCT state in the sensitization. The radiative lifetime (0.84(7) ms) for EuL in the solid state was rather short compared to those of reported Eu(III) complexes. Our results show that the Yb(III) complex with the Schiff base ligand has two features: the short radiative lifetime and the non-triplet sensitization path.     

Role and Perspective of Molecular Simulation-Based Investigation of RNA–Ligand Interaction: From Small Molecules and Peptides to Photoswitchable RNA Binding

Aberrant RNA–protein complexes are formed in a variety of diseases. Identifying the ligands that interfere with their formation is a valuable therapeutic strategy. Molecular simulation, validated against experimental data, has recently emerged as a powerful tool to predict both the pose and energetics of such ligands. Thus, the use of molecular simulation may provide insight into aberrant molecular interactions in diseases and, from a drug design perspective, may allow for the employment of less wet lab resources than traditional in vitro compound screening approaches. With regard to basic research questions, molecular simulation can support the understanding of the exact molecular interaction and binding mode. Here, we focus on examples targeting RNA–protein complexes in neurodegenerative diseases and viral infections. These examples illustrate that the strategy is rather general and could be applied to different pharmacologically relevant approaches. We close this study by outlining one of these approaches, namely the light-controllable association of small molecules with RNA, as an emerging approach in RNA-targeting therapy.     

Polyphenols and Visual Health: Potential Effects on Degenerative Retinal Diseases

Dietary polyphenols are a group of natural compounds that have been proposed to have beneficial effects on human health. They were first known for their antioxidant properties, but several studies over the years have shown that these compounds can exert protective effects against chronic diseases. Nonetheless, the mechanisms underlying these potential benefits are still uncertain and contradictory effects have been reported. In this review, we analyze the potential effects of polyphenol compounds on some visual diseases, with a special focus on retinal degenerative diseases. Current effective therapies for the treatment of such retinal diseases are lacking and new strategies need to be developed. For this reason, there is currently a renewed interest in finding novel ligands (or known ligands with previously unexpected features) that could bind to retinal photoreceptors and modulate their molecular properties. Some polyphenols, especially flavonoids (e.g., quercetin and tannic acid), could attenuate light-induced receptor damage and promote visual health benefits. Recent evidence suggests that certain flavonoids could help stabilize the correctly folded conformation of the visual photoreceptor protein rhodopsin and offset the deleterious effect of retinitis pigmentosa mutations. In this regard, certain polyphenols, like the flavonoids mentioned before, have been shown to improve the stability, expression, regeneration and folding of rhodopsin mutants in experimental in vitro studies. Moreover, these compounds appear to improve the integration of the receptor into the cell membrane while acting against oxidative stress at the same time. We anticipate that polyphenol compounds can be used to target visual photoreceptor proteins, such as rhodopsin, in a way that has only been recently proposed and that these can be used in novel approaches for the treatment of retinal degenerative diseases like retinitis pigmentosa; however, studies in this field are limited and further research is needed in order to properly characterize the effects of these compounds on retinal degenerative diseases through the proposed mechanisms.     

Four Metal Complexes Based on Bulky Imidazole Ligands: Solvothermal Syntheses,Crystal Structures,and Fluorescence Properties

In order to explore the influences of (de‐)protonation of the imidazole ring on the structural diversity of the resulting complexes, the imidazole‐based ligands 4, 5‐diphenylimidazole (Hdpi) and 1H‐phenanthro[9, 10‐d]imidazole (Hpi) were utilized as bulky building blocks to construct four complexes by solvothermal reactions, i.e. [Ag(Hdpi)₂](NO₃) · (H₂O) ( 1 ), [Cu(dpi)]_∞ ( 2 ), [Cu(Hpi)(NO₃)]_∞ ( 3 ), and [(H₂pi)(NO₃)] · H₂O ( 4 ). In complex 1 , two Hdpi ligands adopt a monodentate pattern and coordinate with one Ag^I ion to form a mononuclear unit, which is further connected by hydrogen bonds into a 1D supramolecular helix. The deprotonated dpi ligand of 2 acts in bidentate mode, and bridges Cu^I ions to afford a 1D chain. In 3 , the NO₃^– ion, acts as a monodentate bridging ligand and joins Cu^I ions to generate a 1D chain. The Hpi ligand employs a monodentate mode to bond with Cu^I ions of the 1D chain. 4 is protonated and two H₂pi nitrogen atoms are free of coordination. Interestingly, hydrogen bonds among the NO₃^– ion, the H₂pi ligand, and the water molecule yield a macro ring R⁴₄(14). The resulting structural diversity reveals that the (de‐)protonation of imidazole ring directly steers the coordination number of ligand, and thus causes a significant effect on the structure, especially the dimensionality. Furthermore, the solid‐state fluorescence properties of the free ligands and compounds 1 – 4 were studied at room temperature.     

Different Types of Nickel,Cobalt, and Manganese Complexes originating from 2‐Imidazolecarboxaldiimine of Triethylenetetraamine

The reactivity of the 2‐imidazolecarboxaldiimine of triethylenetetraamine (H2imida) towards divalent manganese, cobalt, and nickel ions differs. It forms a cationic nickel(II) complex by acting as a hexa‐dentate ligand, whereas the cobalt(II) complex formation took place by deprotonation of the H2imida forming a neutral complex with imida. Deprotonation of the ligand by H2imida by cobalt(II) ions caused quenching of the fluorescence emission at 312 nm, such a quenching effect was not observed with the nickel ions. On the other hand, a mononuclear manganese(II) complex of a new tetradentate ligand was formed by manganese(II) assisted intramolecular cyclization reactions of H2imida.     

Solvothermal Syntheses,Crystal Structures,and Luminescent Properties of Two New Cadmium(II) Coordination Polymers Based on Rigid / Flexible Dicarboxylate and N,N′‐Bis(4‐pyridyl)‐1,4,5,8‐naphthalenetetracarboxydiimide

In order to investigate the effect of the organic ligands on the structures of coordination polymers, two new cadmium(II) coordination polymers based on the different dicarboxylate ligands, namely [Cd₂(bpdc)₂(DPNDI)₂] · 3H₂O · NMF ( 1 ) and [Cd(obb)(DPNDI)] ( 2 ) [H₂bpdc = biphenyl‐4,4′‐dicarboxylate, H₂obb = 4,4′‐oxybis(benzoic acid), DPNDI = N,N′‐bis(4‐pyridyl)‐1,4,5,8‐naphthalene tetracarboxydiimide, and NMF = N‐methylformamide), were synthesized under solvothermal condition and further characterized. Complex 1 shows a twofold interpenetrated pcu topology. Complex 2 possesses a two‐dimensional (2D) layer structure with –ABCD– stacking sequence. Furthermore, the luminescent properties of complexes 1 and 2 are investigated.     

Ni(II), Co(II), and Cu(II) complexes incorporating 2-pyrazinecarboxylic acid：Synthesis,characterization, electrochemical evaluation,and catalytic activity for the synthesis of 2H-indazolo[2,1-b]phthalazine-triones

Three complexes containing 2-pyrazinecarboxylate (pzca–), including [Ni(pzca)2(H2O)2], [Co(pzca)2(H2O)2], and [Cu(pzca)2(H2O)2], have been synthesized and characterized using physico-chemical and spectroscopic methods. Furthermore, the structure of each complex was determined by single-crystal X-ray diffraction. All three complexes have an octahedral geometry, where the metal ion chelated by two carboxylate oxygens, two nitrogen atoms belonging to pyrazinic acid molecules, and two oxygen atoms of two water molecules. The catalytic activities of these complex-es were also investigated in the green synthesis of 2H-indazolo[2,1-b]phthalazine-triones by the reaction of hydrazine hydrate with an arylaldehyde, phthalic anhydride, and dimedone in acetic acid.     

铜催化α-重氮酮对硼氢键的不对称插入反应

手性有机硼化合物在有机合成、医药、材料等诸多领域中有广泛的应用,发展该类化合物的高效合成方法一直广受关注.此前,我们发展了过渡金属催化卡宾对硼氢键(B—H)的插入反应,并实现了α-重氮酯对B—H键的不对称插入反应.本文以手性螺环双噁唑啉配体和铜的络合物作为催化剂,首次实现了α-重氮酮对膦-硼烷加合物的B—H键不对称插入反应,获得了较高的收率和高达83%ee的对映选择性.该研究成果是为数不多的以α-重氮酮作为卡宾前体的不对称杂原子氢键插入反应,为手性α-硼取代酮化合物这类新的有机硼化合物的合成提供了有效方法.     

FI催化剂配体的研究进展

FI催化剂作为一类新型聚烯烃催化剂,具有高活性、耐高温等特性,在催化聚合方面表现出良好的性能,不但可以催化乙烯与极性及非极性单体共聚,而且可以通过改变主催化剂苯氧基亚胺配体的结构,得到具有不同结构的聚合物。本文介绍了FI主催化剂的基本结构、合成方法、结构与催化性能的关系以及基于苯氧基亚胺配体基本结构的新型催化剂的研究进展。