Angewandte Chemie International Edition最新文献

The zwitterionic compounds [(LC)P=CS(LC/P)]+ (3+, LC = NHC, LP = PR3), featuring cationic substituents at the phosphorus and carbon atoms, are synthesized as their triflate salts at a multi-gram scale from the reaction of Lewis base adducts of CS2, namely LC/P-CS2 (4), with a combination of [(LCP)4][OTf]4 (1[OTf]4) and Ph3P. The feasibility of using 3+ as PCS building blocks is showcased in their reactions with representative electrophiles (MeOTf) and nucleophiles (MesMgBr, Ph3PCH2), leading to selective functionalization of the PCS core at the S- and P-terminus, respectively. Additionally, it is reported that 3+ can function as ambident nucleophiles with AgOTf (2 equivalents), affording unprecedented linear coordination polymer [Ag2(OTf)3-μ2:κP,κS-((LC)P=CS(PCy3))]+ (6b), where the PCS moiety acts as a bridging ligand in transition metal complexes for the first time. Reduction of 3+ facilitates the cleavage of the P- and C-bound substituents leading to the formation of the [PCS]- anion. Moreover, cycloaddition reactions of 3+ with 1[OTf]4 are shown to selectively yield five- and eight-membered polyphosphorus heterocycles. Preliminary results suggest the possibility of activating the C-S bond in [(LC)P=CS(LC)]+, resulting in the formation of [(LC)P=C(LC)-P(LC)][OTf]2, 12[OTf]2, which may serve as a synthon for the PCP unit in future studies.

The reducing power of iodide anion is an underexplored property that can be used for the cross-electrophile coupling of organic molecules. Herein we harness this trait for the preparation of tertiary amines through the combination of two simple reagents: an electrophilic-carbon precursor and an iminium iodide in a dual role-both as nitrogen-containing building block and as reducing agent. The underlying mechanism of this new C-C bond-formation paradigm is explored through a combination of experiment and quantum chemical calculations.

Understanding photoreaction dynamics in crystals is important for predicting the dynamic property changes accompanying these photoreactions. In this work, we investigate the photoreaction dynamics of p-phenylenediacrylic acid dimethyl ester (p-PDAMe) in single crystals that show reaction front propagation, in which the photoreaction proceeds heterogeneously from the edge to the center of the crystal. Moreover, we find that p-PDAMe single crystals exhibit a distinctive crystal shape change from a parallelogram to a distorted shape resembling a fluttering flag, then to a rectangle as the photoreaction proceeds. Density functional theory calculations predict the crystal structure after the photoreaction, providing a reasonable explanation of the distinctive crystal shape change that results from the spatially heterogeneous photoreaction. These results prove that the spatially heterogeneous photoreaction dynamics have the ability to induce novel crystal shape changes beyond what would be expected based on the equilibrium reactant and product crystal shapes.

Tetrachlorides of zirconium- and hafnium form adducts (2, 3) with an intramolecular germylene phosphine Lewis pair. Two electron reduction treating the adducts with [MesNacnacMg]2 gives the low valent metal complexes (4, 5) featuring η6-Trip coordination at the Zr(II) and Hf(II) metal atom. Reduction of the M(II)-complexes gives the zerovalent metal complexes of zirconium (6) and hafnium (7), which have been structurally characterized. Two arene moieties and the germylene exhibit metal coordination. Puckered coordination of a P-phenyl unit was observed for both derivatives 6 and 7. Four electron reduction of a reaction mixture of metal tetrachloride with the germylene-phosphine Lewis pair also gives the zerovalent complexes in good yield. Carbonyl complexes were synthesized treating the reduced metal complexes with carbon monoxide. Dimethylbutadiene shows a reaction with an arene moiety and the coordinated germylene ligand of the zerovalent complexes. A cyclohexadienyl and a triorganogermate ligand are formed. For zirconium this reaction is reversible at room temperature.

The synergetic evolution of multiple chiral structures stemmed from same building units is ubiquitous in nature and vital to living systems, but achieving it in artificial systems remains a challenge. Herein, we report a methanol-water mediated dual assembly pathway strategy for simultaneous construction of P and M helices in one-component chiral system. The conformation of l-phenylaniline derivates (LBpyF) is controlled to folded state in CH3OH due to the hydrogen bonds as well as C-H···π interaction between LBpyF and CH3OH. Addition of H2O into above CH3OH solution of LBpyF results in the simultaneous occurrence of two self-assembly pathways and double networks of P and M helices were therefore formed, due to the synchronous process of 1) self-assembly of folded LBpyF into M-helices and 2) H2O induced unfolding of folded LBpyF molecules followed by self-assembly of them into P-helices. The bipyridine core, phenyl ring, amide unit all adapted into different stacking modes in M-helices and P-helices, and energy analysis indicated that the minority M-helices were more thermodynamically favored products. This study provides an approach to explore synergetic evolution of multiple chiral structures by manipulating the multiple assembly pathway.

Malignant tumors pose a significant threat to global public health. Promoting programmed cell death in cancer cells has become a critical strategy for cancer treatment. PANoptosis, a newly discovered form of regulated cell death, integrates key molecular components of pyroptosis, apoptosis, and necroptosis, activating these three death pathways simultaneously to achieve synergistic multi-mechanistic killing. PANoptosis significantly inhibits cancer cell growth and resistance, making tumor-specific induction of PANoptosis a potential cancer therapeutic strategy. Currently, cancer treatment research related to PANoptosis is mainly focused on the development of small molecules and cytokines. However, these approaches still face limitations in terms of metabolic stability and tumor specificity. The development of nanotechnology offers new opportunities for cancer treatment by improving targeting efficiency, extending circulation time, and enhancing therapeutic efficacy and safety. Additionally, the unique physicochemical properties of nanomaterials can effectively optimize PANoptosis induction strategies, establishing nanomaterials as ideal candidates for inducing PANoptosis in tumor cells. This review summarizes the concept and mechanisms of PANoptosis, highlights the latest applications of nanoagents in PANoptosis-based anti-cancer therapy, and discusses the challenges and future directions for clinical translation. This review will inspire further exploration and development of PANoptosis-based cancer treatments, providing new perspectives for researchers in the field.

"The most important future application of my research is the optical readout of magnetic memories without the need for light polarization devices… My biggest motivation is to make sound science, appreciated by other scientists…" Find out more about Matteo Atzori in his Introducing… Profile.