Copper‐Catalyzed Heteroarylboration of 1,3‐Dienes with 3‐Bromopyridines: A cine Substitution

A method for the heteroarylboration of 1,3‐dienes is presented. The process involves an unusual cine substitution of 3‐bromopyridine derivatives to deliver highly functionalized heterocyclic products. Mechanistic studies are included that clarify the details of this unusual process.     

Bottleable Neutral Analogues of [B2H5]− as Versatile and Strongly Binding η2 Donor Ligands

Herein we report the discovery that two bottleable, neutral, base‐stabilized diborane(5) compounds are able to bind strongly to a number of copper(I) complexes exclusively through their B?B bond. The resulting complexes represent the first known complexes containing unsupported, neutral σ_B?B diborane ligands. Single‐crystal X‐ray analyses of these complexes show that the X?Cu moiety (X=Cl, OTf, C₆F₅) lies opposite the bridging hydrogen atom of the diborane and is near perpendicular to the B?B bond, interacting almost equally with both boron atoms and causing a B?B bond elongation. DFT studies show that σ donation from and π backdonation to the pseudo‐π‐like B?B bond account for their formation. Astoundingly, these copper σ_B?B complexes are inert to ligand exchange with pyridine under either heating or photoirradiation.     

Electrochemical C−H Amination by Cobalt Catalysis in a Renewable Solvent

Syntheses of substituted anilines primarily rely on palladium‐catalyzed coupling chemistry with prefunctionalized aryl electrophiles. While oxidative aminations have emerged as powerful alternatives, they largely produce undesired metal‐containing by‐products in stoichiometric quantities. In contrast, described herein is the unprecedented electrochemical C?H amination by cobalt‐catalyzed C?H activation. The environmentally benign electrocatalysis avoids stoichiometric metal oxidants, can be conducted under ambient air, and employs a biomass‐derived, renewable solvent for sustainable aminations in an atom‐ and step‐economical manner with H₂ as the sole byproduct.     

Optically Matched Semiconductor Quantum Dots Improve Photophosphorylation Performed by Chloroplasts

A natural–artificial hybrid system was constructed to enhance photophosphorylation. The system comprises chloroplasts modified with optically matched quantum dots (chloroplast–QD) with a large Stokes shift. The QDs possess a unique optical property and transform ultraviolet light into available and highly effective red light for use by chloroplasts. This favorable feature enables photosystem II contained within the hybrid system to split more water and produce more protons than chloroplasts would otherwise do on their own. Consequently, a larger proton gradient is generated and photophosphorylation is improved. At optimal efficiency activity increased by up to 2.3 times compared to pristine chloroplasts. Importantly, the degree of overlap between emission of the QDs and absorption of chloroplasts exerts a strong influence on the photophosphorylation efficiency. The chloroplast–QD hybrid presents an efficient solar energy conversion route, which involves a rational combination of a natural system and an artificial light‐harvesting nanomaterial.     

Exposing the Origins of Irreproducibility in Fluorine NMR Spectroscopy

Fluorine chemistry has taken a pivotal role in chemical reaction discovery, drug development, and chemical biology. NMR spectroscopy, arguably the most important technique for the characterization of fluorinated compounds, is rife with highly inconsistent referencing of fluorine NMR chemical shifts, producing deviations larger than 1 ppm. Herein, we provide unprecedented evidence that both spectrometer design and the current unified scale system underpinning the calibration of heteronuclear NMR spectra have unintentionally led to widespread variation in the standardization of ¹⁹F NMR spectral data. We demonstrate that internal referencing provides the most robust, practical, and reproducible method whereby chemical shifts can be consistently measured and confirmed between institutions to less than 30 ppb deviation. Finally, we provide a comprehensive table of appropriately calibrated chemical shifts of reference compounds that will serve to calibrate ¹⁹F spectra correctly.     

Photocontrolled Multidirectional Differentiation of Mesenchymal Stem Cells on an Upconversion Substrate

The effective guidance of mesenchymal stem cell (MSC) differentiation on a substrate by near‐infrared (NIR) light is particularly attractive for tissue engineering and regenerative medicine. However, most of current substrates cannot control multidirectional differentiation of MSCs like natural tissues. Herein, a photocontrolled upconversion‐based substrate was designed and constructed for guiding multidirectional differentiation of MSCs. The substrate enables MSCs to maintain their stem‐cell characteristics due to the anti‐adhesive effect of 4‐(hydroxymethyl)‐3‐nitrobenzoic acid modified poly(ethylene glycol) (P1) attached on the upconversion substrate. Upon NIR irradiation, the P1 is released from the substrate by photocleavage. The detachment of P1 can change cell–matrix interactions dynamically. Moreover, MSCs cultured on the upconversion substrate can be specifically induced to differentiate to adipocytes or osteoblasts by adjusting the NIR laser. Our work provides a new way of using NIR‐based upconversion substrate to modulate the multidirectional differentiation of MSCs.     

Sodiation of Arenes and Heteroarenes in Continuous Flow

The first sodiations of (hetero)arenes in continuous flow using NaDA (sodium diisopropylamide) in Me₂EtN are reported. This flow procedure enables sodiation of functionalized arenes and heteroarenes that decompose under batch‐sodiation conditions. The resulting sodiated (hetero)arenes react instantly with various electrophiles, such as ketones, aldehydes, isocyanates, alkyl bromides, and disulfides, affording polyfunctionalized (hetero)arenes in high yields. Scale‐up is possible without further optimization.     

Monochalcoplatin: An Actively Transported,Quickly Reducible,and Highly Potent PtIV Anticancer Prodrug

Recently, Pt^IV prodrugs have attracted much attention as the next generation of platinum‐based antineoplastic drug candidates. Here we report the discovery and evaluation of monochalcoplatin, a monocarboxylated Pt^IV prodrug that is among the most cytotoxic Pt^IV prodrugs to date. Compared with its dicarboxylated counterpart chalcoplatin, monochalcoplatin accumulates astonishingly effectively and rapidly in cancer cells, which is not ascribed to its lipophilicity. The prodrug is quickly reduced, causes DNA damage, and induces apoptosis, resulting in superior cytotoxicity with IC₅₀ values in the nanomolar range in both cisplatin‐sensitive and ‐resistant cells; these IC₅₀ values are up to 422‐fold higher than that of cisplatin. A detailed mechanistic study reveals that monochalcoplatin actively enters cells through a transporter‐mediated process. Moreover, monochalcoplatin shows significant antitumor activity in an in vivo colorectal tumor model. Our study implies a practical strategy for the design of more effective Pt^IV prodrugs to conquer drug resistance by tuning both cellular uptake pathways and activation processes.     

Steric Effect of Carboxylate Ligands on Pd‐Catalyzed Intramolecular C(sp2)–H and C(sp3)–H Arylation Reactions

A bulky carboxylic acid bearing three cyclohexylmethyl substituents at the α‐position, namely, tri(cyclohexylmethyl)acetic acid, is demonstrated to act as an efficient ligand source in Pd‐catalyzed intramolecular C(sp²)?H and C(sp³)?H arylation reactions. The reactions proceed smoothly under mild reaction conditions, even at room temperature due to the steric bulk of the carboxylate ligands, which accelerates the rate‐determining C?H bond activation step in the catalytic cycle.     

A Microporous Covalent–Organic Framework with Abundant Accessible Carbonyl Groups for Lithium‐Ion Batteries

A key challenge faced by organic electrodes is how to promote the redox reactions of functional groups to achieve high specific capacity and rate performance. Here, we report a two‐dimensional (2D) microporous covalent–organic framework (COF), poly(imide‐benzoquinone), via in situ polymerization on graphene (PIBN‐G) to function as a cathode material for lithium‐ion batteries (LIBs). Such a structure favors charge transfer from graphene to PIBN and full access of both electrons and Li⁺ ions to the abundant redox‐active carbonyl groups, which are essential for battery reactions. This enables large reversible specific capacities of 271.0 and 193.1 mAh g^?1 at 0.1 and 10 C, respectively, and retention of more than 86 % after 300 cycles. The discharging/charging process successively involves 8 Li⁺ and 2 Li⁺ in the carbonyl groups of the respective imide and quinone groups. The structural merits of PIBN‐G will trigger more investigations into the designable and versatile COFs for electrochemistry.