Electrochemical α-C(sp)-H/N-H Cross-Coupling of Isochromans and Azoles.

Isochroman and azole moieties are both present in a wide variety of biologically active molecules. Their efficient combination under mild reaction conditions is beneficial for obtaining small-molecule drug candidates. In this paper, we describe electrochemical α-C(sp)-H/N-H cross-coupling reactions between isochromans and azoles, yielding products in moderate to excellent yields.

Ultra-High Metal-Ion Selectivity Induced by Intramolecular Cation-π Interactions for the One-Pot Synthesis of Precise Heterometallic Architectures.

Heterometallic supramolecules, known for their unique synergistic effects, have shown broad applications in photochemistry, host-guest chemistry, and catalysis. However, there are great challenges to precisely construct heterometallic supramolecules rather than a statistical mixture, due to the limited metal-ion selectivity of coordination units. In particular, heterometallic architectures precisely encoded with different metal ions usually fail to form in a one-pot method when only one type of coordinated motif exists due to its poor metal-ion selectivity.

Synthesis, Characterization, and Catalytic Behaviors in Isoprene Polymerization of Pyridine-Oxazoline-Ligated Cobalt Complexes.

A family of pyridine-oxazoline-ligated cobalt complexes LCoCl- were synthesized and characterized. Determined via single-crystal X-ray diffraction, complexes and ligated by two ligands, displayed a distorted tetrahedral coordination of a cobalt center. The X-ray structure indicated the pyridine-oxazoline ligands acted as unusual mono-dentate ligands by coordinating only to N.

Visual Gustation via Regulable Elastic Photonic Crystals.

The unique structural sensitivity of photonic crystals (PCs) endows them with stretchable or elastic tunability for light propagation and spontaneous emission modulation. Hydrogel PCs have been demonstrated to have biocompatibility and flexibility for potential human health detection and environmental security monitoring. However, current elastic PCs still possess a fixed elastic modulus and uncontrollable structural colors based on a tunable elastic modulus, posing considerable challenges for in situ detection, particularly in wearable or portable sensing devices.

Cu(II)-Mediated Sulfonylation of (Hetero)arenes with TosMIC Using Monodentate Directing Groups.

Monodentate chelation-assisted direct -C-H sulfonylation of (hetero)arenes using TosMIC as the novel sulfonylating reagent has been developed. A broad range of substrates, including indolines, indoles, 2-phenylpyridines, and others were well tolerated to afford the corresponding products in moderate to good yields. Mechanistic studies revealed that the sulfonyl radical might be involved.

Construction of 1,3,5-Triazine-Based Prisms and Their Enhanced Solid-State Emissions.

In this study, two trigonal prisms based on the 1,3,5-triazine motif ( and ), distinguished by hydrophobic groups, were prepared by the self-assembly of tritopic terpyridine ligands and Zn(II) ions. and exhibited high luminescence efficiencies in the solid state, overcoming the fluorescence quenching of the 1,3,5-triazine group caused by π-π interactions. Notably, and exhibited different luminescence behaviors in the solution state and aggregation state.

Hourglass-Shaped Nanocages with Concaved Structures Based on Selective Self-Complementary Coordination Ligands and Tunable Hierarchical Self-Assembly.

Three-dimensional (3D) structures constructed via coordination-driven self-assemblies have recently garnered increasing attention due to the challenges in structural design and potential applications. In particular, developing new strategy for the convenient and precise self-assemblies of 3D supramolecular structures is of utmost interest. Introducing the concept of self-coordination ligands, herein the design and synthesis of two meta-modified terpyridyl ligands with selective self-complementary coordination moiety are reported and their capability to assemble into two hourglass-shaped nanocages SA and SB is demonstrated.

Amine-Imine Nickel Catalysts with Pendant O-Donor Groups for Ethylene (Co)Polymerization.

The introduction of a secondary interaction is an efficient strategy to modulate transition-metal-catalyzed ethylene (co)polymerization. In this contribution, O-donor groups were suspended on amine-imine ligands to synthesize a series of nickel complexes. By adjusting the interaction between the nickel metal center and the O-donor group on the ligands, these nickel complexes exhibited high activities for ethylene polymerization (up to 3.

Tailored Supramolecular Cage for Efficient Bio-Labeling.

Fluorescent chemosensors are powerful imaging tools used in a broad range of biomedical fields. However, the application of fluorescent dyes in bioimaging still remains challenging, with small Stokes shifts, interfering signals, background noise, and self-quenching on current microscope configurations. In this work, we reported a supramolecular cage () by coordination-driven self-assembly of benzothiadiazole derivatives and Eu(OTf).

Water-Soluble Metallo-Supramolecular Nanoreactors for Mediating Visible-Light-Promoted Cross-Dehydrogenative Coupling Reactions.

Water-soluble metallo-supramolecular cages with well-defined nanosized cavities have a wide range of functions and applications. Herein, we design and synthesize two series of metallo-supramolecular octahedral cages based on the self-assembly of two congeneric truxene-derived tripyridyl ligands modified with two polyethylene glycol (PEG) chains, i.e.

A Cavity-Tailored Metal-Organic Tetrahedral Nanocage and Gas Adsorption Property.

Porous organometallic nanomaterials are a new class of materials based on a three-dimensional structure. They have excellent applications in different fields, but their applications in gas storage and separation have not been fully developed. CO adsorption storage and hydrocarbon separation has been a challenging industrial problem.

Synthesis of a Tetrahedral Metal-Organic Supramolecular Cage with Dendritic Carbazole Arms.

In recent years, incredible endeavors have been devoted to the design and self-assembly of discrete metal-organic cages (MOCs) with expanding intricacy and functionality. The controlled synthesis of metal-organic supramolecular cages with large branched chains remains an interesting and challenging work in supramolecular chemistry. Herein, a tetrahedral metal-organic supramolecular cage (ZnL) containing 12 dendritic carbazole arms is unprecedentedly constructed through coordination-driven subcomponent self-assembly and characterized in different ways.

Construction of metallo-triangles with -TPE motifs and fluorescence properties.

Two metallo-triangles, SA and SB, with -TPE motifs were constructed, and their fluorescence properties were explored. Compared with the dilute solution, both triangles SA and SB exhibited significant AIE behavior in the aggregated states. Moreover, the shorter version SA showed higher quantum yields than SB in the aggregated states.

New NNN pincer copper complexes as potential anti-prostate cancer agents.

Eleven novel NNN Cu(II) complexes supported by a tridentate bis(imidazo[1,2-α]pyridin-2-yl)pyridine ligand were synthesized and characterized by elemental analysis, HRMS, and X-ray determination. Target prediction and docking studies indicated that these pincer complexes formed hydrogen bonds with Asp33 and Gly35 of Cathepsin D protein, which is highly associated with prognosis of advanced prostate cancer. Furthermore, they exhibited anti-proliferation activity in both androgen-sensitive and androgen-insensitive prostate cancer cells according to WST-1 assay results.

The Novel Function of Unsymmetrical Chiral CCN Pincer Nickel Complexes as Chemotherapeutic Agents Targeting Prostate Cancer Cells.

We report that the pincer nickel complexes display prostate cancer antitumor properties through inhibition of cell proliferation. Notably, they display better antitumor properties than cisplatin. Mechanistic studies reveal that these pincer nickel complexes trigger cell apoptosis, most likely due to cell cycle arrest.

Design and Self-Assembly of Macrocycles with Metals at the Corners Based on Dissymmetric Terpyridine Ligands.

Terpyridine-based discrete supramolecular architectures with metal ions at the corners have rarely been reported. Herein, we report two dissymmetric terpyridyl ligands LA and LB decorated at the 5-position and 4-position of terpyridine respectively. The complexes constructed by the self-assembly of LA and LB with Zn(II) exhibit hand-circle-like structures.

Cu(II)-Catalyzed N-Directed Distal C(sp)-H Heteroarylation of Aliphatic -Fluorosulfonamides.

A copper-catalyzed δ-regioselective C(sp)-H heteroarylation of -fluorosulfonamides has been developed. A broad range of heteroarenes were well tolerated and reacted with various -fluorosulfonamides to give the corresponding heteroarylated amides in good yields. Notably, all types (1°, 2°, and 3°) of δ-C(sp)-H bonds in the -fluorosulfonamides could be regioselectively activated through the 1,5-HAT process.

Fe(III)-Catalyzed -Amidomethylation of Secondary and Primary Anilines with TosMIC.

A Fe(III)-catalyzed -amidomethylation of secondary and primary anilines with -toluenesulfonylmethyl isocyanide (TosMIC) in water is described. TosMIC plays dual roles as the source of methylene as well as an amidating reagent to form α-amino amides in this multicomponent reaction. The combination of TosMIC and other isocyanides was also investigated to give the desired products in acceptable yields.

Designing narcissistic self-sorting terpyridine moieties with high coordination selectivity for complex metallo-supramolecules.

Coordination-driven self-assembly is a powerful approach for the construction of metallosupramolecules, but designing coordination moieties that can drive the self-assembly with high selectivity and specificity remains a challenge. Here we report two ortho-modified terpyridine ligands that form head-to-tail coordination complexes with Zn(II). Both complexes show narcissistic self-sorting behaviour.

Aspulvinones Suppress Postprandial Hyperglycemia as Potent α-Glucosidase Inhibitors From ASM-1.

Chemical investigation of ASM-1 fermentation resulted in the isolation of three new prenylated aspulvinones V-X (-), together with the previously reported analogs, aspulvinone H (), J-CR (), and R (). Their structures were elucidated by various spectroscopic methods including HRESIMS and NMR, and the absolute configurations of and were determined by ECD comparison. Compounds - were evaluated for α-glucosidase inhibitory effects with acarbose as positive control.

Regioselective N-F and α C(sp)-H Arylation of Aliphatic -Fluorosulfonamides with Imidazopyridines.

A regioselective arylation of aliphatic -fluorosulfonamides with imidazopyridines enabled by breaking of N-F and α C(sp)-H bond to form C-N and C-C bonds was described. With CuCl as the catalyst, a radical mechanism was proposed to produce N-arylated aliphatic sulfonamides via a N radical intermediate. Importantly, under acidic conditions, an in situ generated imine was the possible intermediate, which was trapped by imidazopyridines to form α C(sp)-H arylated aliphatic sulfonamides.

Iron-Mediated Selective Sulfonylmethylation of Aniline Derivatives with -Toluenesulfonylmethyl Isocyanide (TosMIC).

An iron-mediated highly selective C-H sulfonylmethylation of aniline derivatives with -toluenesulfonylmethyl isocyanide in a mixture solvent of HO and PEG under an Ar atmosphere has been realized. This transformation proceeds with operational convenience, use of earth-abundant metal catalyst and nontoxic media, broad substrate scope, and good functional group tolerance. The current methodology could be applied to the regioselective C-H sulfonylmethylation of indolines, tetrahydroquinolines, and tertiary anilines.

Genome-Wide Identification of Brassinosteroid Signaling Downstream Genes in Nine Rosaceae Species and Analyses of Their Roles in Stem Growth and Stress Response in Apple.

Brassinosteroid signaling downstream genes regulate many important agronomic traits in rice. However, information on such genes is limited in and Rosaceae species. We identified these genes in and nine Rosaceae species.

NaOH-Mediated Direct Synthesis of Quinoxalines from -Nitroanilines and Alcohols via a Hydrogen-Transfer Strategy.

A NaOH-mediated sustainable synthesis of functionalized quinoxalines is disclosed via redox condensation of -nitroamines with diols and α-hydroxy ketones. Under optimized conditions, various -nitroamines and alcohols are well tolerated to generate the desired products in 44-99% yields without transition metals and external redox additives.