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Coordination chemistry driven by aurophilic interactions has generated numerous unique supramolecular architectures with tunable structures and innovative functions. In this work, a dimeric cluster-based capsule [C1]2·6PF6− ([(dppmAu2)3L1]2·6PF6−) with a dynamic cavity was self-assembled. The dppmAu2Cl2 dinuclear gold(I) complex was used as the coordination corner and the K3L1 (1, 3, 5-tri(1-bicarbodithiolate piperazinyl)-2,4,6-triethylbenzene potassium salt) tripodal cavitand acted as the organic linker in a multiple-component modular synthesis strategy. A tetranuclear gold(I) corner with a continuous AuI⋯AuI bonding motif was formed during the self-assembly and crystallization process of a [Au6L1]-type semispherical monomeric cluster that was spontaneously aggregated into a [Au6L1]2-type dimeric capsule. The AuI⋯AuI coupling molecular capsule exhibited excellent photophysical properties and electron–hole separation ability. Accordingly, the photocatalytic performance for the benzylamine oxidation coupling reaction was outstanding. For ten aromatic amine substrates, the catalytic yield reached 88–96% under irradiation. In addition, the recycled catalytic yield remained above 86% after three runs due to the high chemical stability and tolerance of the [C1]2·6PF6− cluster catalyst. In the photocatalytic mechanism, the primary amines formed holes, thereby triggering amine substrate oxidation, reactive oxygen species (ROS)-induced C–N bond activation, and imine condensation. Here, the formation of the intermediate benzaldehyde was detected using real-time 1H-NMR monitoring and electrospray ionization mass spectroscopy (MS), and then further confirmed by density functional theory (DFT) calculations. This dynamic gold(I) cluster-based capsule can potentially be utilized as a photocatalyst via selective host-guest recognition associated with cooperative multi-metal aurophilic interaction. [ABSTRACT FROM AUTHOR]

Ring‐opening transformations of donor‐acceptor (D‐A) cyclopropanes enable the rapid assembly of complex molecules. However, the enantioselective formation of chiral quaternary stereocenters using substrates bearing two different acceptors remains a challenge. Herein, we describe the first palladium‐catalyzed highly diastereo‐ and enantioselective (3+2) cycloaddition of vinyl cyclopropanes bearing two different electron‐withdrawing groups, a subset of D‐A cyclopropanes. The key to the success of this reaction is the remote stereoinduction through hydrogen bond from chiral ligands, which thereby addressed the aforementioned challenge. A variety of chiral five‐membered heterocycles were produced in good yields and with high stereoselectivity (up to 99 % yields, 99 : 1 er and >19 : 1 dr). In‐depth mechanistic investigations, including control experiments and theoretical calculations, revealed the origin of the stereoselectivity and the importance of H‐bonding in stereocontrol. [ABSTRACT FROM AUTHOR]

A novel series of N-methylpicolinamide-4-thiol derivatives were synthesized and evaluated on human cancer cell lines. Among them, compound 6p displayed potent and broad-spectrum anti-proliferative activities in vitro on some human cancer cell lines, even better than sorafenib. The advanced kinase inhibitory assays showed that compound 6p could selectively inhibit Aurora-B kinase. The biological results were rationalized by the molecular docking study, which indicated the stable interactions of 6p with the Aurora-B kinase.

A novel metal–organic cage 1·8PF6− was precisely self-assembled using polynitrogen pyrazine-triazine ligand as linker L1 and bpyPd(NO3)2 as coordination corner (where 1·8PF6− = [(bpyPd)4L12]8+·8PF6−; L1 = 4, 6-bis((pyrazin-2-ylmethyl)amino)-1,3,5-triazin-2-ol); bpy = 2,2′-bipyridine) in aqueous solution. The capsule-like coordination cage 1·8PF6− was fully characterized by single-crystal X-ray diffraction analysis, 1H and 13C-NMR and ESI–MS analysis. In the crystal structure, cage 1 closely stacked into a stable 3D framework structure with a regular channel. By employment of such crystalline adsorbent material, permanganate anion (MnO4−) can be rapidly adsorbed into cationic channel and exchanged with hexafluorophosphate anion from water, in which the crystallinity of cage 1 remained unaffected before and after adsorption. Moreover, the anion adsorption and exchanging behavior was revealed by Fourier transform infrared spectra (FTIR), powder X-ray diffraction analysis (PXRD), scanning electron microscopy (SEM), electron adsorption and fluorescence spectroscopy. [ABSTRACT FROM AUTHOR]

There are two molecules in the asymmetric unit molecule of the title compound, C8H10ClN3O2. Intramolecular N—H...O hydrogen bonds stabilize the molecular structure. There are no classical intermolecular hydrogen bonds in the crystal structure.

There are two independent molecules in the asymmetric unit of the title compound, C22H21N3O4S. The central benzene ring makes dihedral angles of 74.28 (6) and 68.84 (6)° with the pyridine and 3,5-dimethoxyphenyl rings, respectively, in one molecule [86.66 (6) and 81.14 (6)° respectively, in the other]. Each of the molecules forms a centrosymmetric dimer with another molecule via pairs of intermolecular N—H...O hydrogen bonds. These hydrogen bonds connect the N—H groups and the O atoms of the carbonyl groups next to the 3,5-dimethoxyphenyl rings. Additional intermolecular N—H...O interactions link the dimers in the crystal structure.

A novel series of N-methylpicolinamide-4-thiol derivatives were synthesized and evaluated on human cancer cell lines. Among them, compound 6p displayed potent and broad-spectrum anti-proliferative activities in vitro on some human cancer cell lines, even better than sorafenib. The advanced kinase inhibitory assays showed that compound 6p could selectively inhibit Aurora-B kinase. The biological results were rationalized by the molecular docking study, which indicated the stable interactions of 6p with the Aurora-B kinase. [ABSTRACT FROM AUTHOR]

Isodesmic reactions, in which chemical bonds are redistributed between substrates and products, provide a general and powerful strategy for both biological and chemical synthesis. However, most isodesmic reactions involve either metathesis or functional-group transfer. Here, we serendipitously discovered a novel isodesmic reaction of indoles and anilines that proceeds intramolecularly under weakly acidic conditions. In this process, the five-membered ring of the indole motif is broken and a new indole motif is constructed on the aniline side, accompanied by the formation of a new aniline motif. Mechanistic studies revealed the pivotal role of σ→π* hyperconjugation on the nitrogen atom of the indole motif in driving this unusual isodesmic reaction. Furthermore, we successfully synthesized a diverse series of polycyclic indole derivatives; among quinolines, potential antitumor agents were identified using cellular and in vivo experiments, thereby demonstrating the synthetic utility of the developed methodology., (© 2024 Wiley‐VCH GmbH.)