The chiral cyclopropane framework is a crucial structural motif in bioactive molecules such as pharmaceuticals and natural products. Asymmetric cyclopropanation of alkenes via transition metal-catalyzed carbene transfer represents one of the most direct approaches for synthesizing chiral cyclopropanes. While significant progress has been made in the asymmetric cyclopropanation of α-C-substituted carbenes, the highly enantioselective cyclopropanation of α-silyl carbenes, which possess greater transformation potential, remains largely unexplored. In this study, we report a Cu(I)/chiral bisoxazoline catalytic system that enables highly enantioselective cyclopropanation and cyclopropanation/Cope rearrangement reactions between α-silyl-α-alkenyl carbenes (generated from ring opening of 1-silyl cyclopropene) and alkenes. This methodology provides access to a series of chiral cyclopropylsilanes containing stereogenic quaternary carbon centers as well as allylic silane moieties and chiral cycloheptadienylsilanes, thereby expanding the diversity of chiral organosilicon compounds. Theoretical calculations reveal that the rate-determining step involves the ring opening of cyclopropene, where the silyl group not only dictates the regioselectivity of the ring opening but also significantly influences the stereoselectivity of the reaction through its steric and rigid properties.

The primary objective of this study is to thoroughly explore the processes of homogeneous nucleation in alloys and heterogeneous nucleation in organic heterostructures, with the ultimate goal of gaining precise control over the selection between two nucleation mechanisms. By using Perylene (Pe) as the donor and isomers of tetrachlorophthalonitrile as the acceptors, alloys with continuously tunable luminescent colors were successfully synthesized in a one-step process. Additionally, using two-step synthesis, microcrystals of triblock and semi-core/shell heterostructures, composed of cocrystals and alloys, were successfully prepared. Notably, the formation of the two types of heterostructures was elucidated, emphasizing the kinetic and thermodynamic effects on the nucleation of cocrystals. Additionally, the heterostructures facilitate the construction of optical logic gates with photonic coding.

OFET-type optical memories using light bias as the fourth terminal enable low voltage electrical stresses to suffice in generating substantial memory window and photoassisted multibit storage. The undefined molecular structure and trapping mechanism of most storage media limit their practical applications. Herein, we report a series of charge trapping materials with the rigid and planar conjugated structure of benzo[1,2-b:4,5-b’]dithiophene (BDT) acting as the charge trapping site and photoresponsive group, while the insulated (triisopropylsilyl)acetylene (TIPS) unit is introduced to prevent the leakage path of the charge. The pentacene-based OFET memory with solution-processing TTIPS-BDT shows fast trapping speed, tunable ambipolar memory, large memory window and reliable charge retention, which is obviously improved compare to the performance of BDT and DTIPS-BDT devices. In addition, the charge trapping, memory characteristics and photoresponsive behaviors are also discussed in detail. The TTIPS-BDT device shows a specific response to green light illumination. This study suggests that BDT derivatives serving as charge trapping elements possess potential applications in future photoresponsive memory and plastic electronics.

Herein, a theory-guided ternary construction case on boosting power conversion efficiency (PCE) for all-polymer solar cell (all-PSC) is reported, where guest acceptor's characteristics include high miscibility with host polymer acceptor, significantly larger optical bandgap, and improved luminescence. Consequently, with only 10 wt% PFFO-Th (third component) addition, the PCE of binary control is promoted to 18.55% from 16.69%, a 11.1% relative increase, demonstrating the great effectiveness of this ternary strategy. Besides, the realized 18.55% efficiency is at state-of-the-art level of all-PSCs processed by ortho-xylene, a widely acknowledged green non- halogenated solvent by the field. This study shares new thought on designing high-performance photovoltaic devices with reduced energy losses and favorable charge dynamics, which would nourish future development on all-PSCs, and even other organic electronics.

The design of ionic hydrogen-bonded organic frameworks (iHOFs) with single crystal superprotonic conductivity is of great significance for studying the mechanism of proton conduction materials at molecular level. To regulate the proton transport path, this study focused on using stereoscopic 2,2',7,7'-tetraphosphone-9,9'-spirofluorene regulated by different lengths of amidine compound to form two chemically identical but structurally different single crystals iHOF-46 and iHOF-47. Both of them have hydrogen bond networks of different dimensions and highly anisotropic proton conductivity, and the clear proton transport path is proposed by analyzing the single crystal structure. Importantly, the experimental results show that iHOF-47 with a two-dimensional (2D) hydrogen bond network has a proton conductivity of up to 0.193 S·cm⁻¹ in the (0, 0, –1) direction at 80 °C and 98% RH. A combination of single-crystal structure analysis and density functional theory (DFT) calculations reveals that iHOF-47 has a very continuous and smooth proton transport path in the direction of (0, 0, –1), and the lower energy barrier required for proton transport leads to higher proton conductivity. This is significant for guiding the unidirectional growth of crystals and establishing a "visible" proton conductivity pathway.

Aromatic polyketides (APKs) are renowned for their structural diversity and potent biological activities, making them valuable resources for drug discovery in antibiotics, anticancer agents, and antiparasitic therapies. Bipentaromycins, a unique class of dimeric APKs with a cyclic head-to-tail linkage, exhibit broad-spectrum antibacterial activities. Acylation modifications in bipentaromycins C–F enhance their pharmacological properties, yet the responsible acyltransferase remains enigmatic. Herein, we present REGAIN, an innovative strategy combining restriction enzyme digestion, Gibson assembly, and in vivo Cre-lox recombination, enabling rapid and efficient cloning of biosynthetic gene clusters (BGCs). Using REGAIN, we successfully cloned a 40 kb bipentaromycin BGC (bpm). By integrating genetic experiments and computational modeling, we speculated BpmP as the acyltransferase responsible for regioselective acylation. This study establishes a robust platform for exploring novel bioactive molecules and advances the understanding of bipentaromycin biosynthesis.

Chiral tricyclic compounds represent a significant class of biologically active substances with wide-ranging applications in materials science, medicinal chemistry, as well as the food and fragrance industries. Here, we combine CAST (combinatorial active site saturation test) and bacterial surface display technology to develop a laboratory-evolved whole-cell catalyst, designated SD-VHb_Tric (surface display of vitreoscilla hemoglobin). This novel carbene-transferase is based on the engineered VHb and employs a strategy for the cyclopropanation of unsaturated π-systems to synthesize various chiral tricyclic structures. SD-VHb_Tric exhibits unparalleled stereocontrol (up to 99.9% de and 99% ee) and good reactivity, enabling the synthesis of chiral tricyclic structures with diverse aromatic or heterocyclic ring scaffolds from simple starting materials. Additionally, computational studies were conducted to elucidate the crucial role of intermolecular hydrophobic interactions in regulating the reaction, while also demonstrating the significant impact of adaptive changes in the active pocket size on the orientation of the ligand.

A desulfonylative thiolation between heteroaryl sulfones and thiosulfonates for the efficient synthesis of heteroaryl sulfides was developed. The cross-electrophile couplings proceeded effectively via old C–SO₂ bond cleavage and new C–S bond formation in the presence of cheapest and widely available iron powder as mediator under transition metal catalyst-free conditions, leading to a wide array of heteroaryl sulfides derived from benzo[d]thiazole, benzo[d]oxazole, thiazole, 1,3,4-thiadiazole, and 1H-tetrazole in modest to excellent yields. In addition, the reaction exhibited good functional group compatibility, and the protocol could also be applicable to the use of selenosulfonate as substrate and be subjected to scale-up synthesis with equal ease. Notably, unreacted iron powder could be readily recovered after reaction by resorting to the attracting property of magnetic stir bar to iron.

An innovative approach to synthesizing pyrrole-functionalized phosphorodithioates via a copper-catalyzed cascade phosphorodithiolation/cyclization of β-ketodinitriles is disclosed. This method employs tetraphosphorus decasulfide (P₄S₁₀) as a phosphorus source, activated by alcohols under mild conditions. A wide range of β-ketodinitriles and alcohols are well-tolerated, affording the desired products with good to excellent yields, underscoring broad functional group compatibility. Notably, this process eschews the need for noble metal catalysts, aligning with green chemistry principles by enabling a direct and sustainable transformation from inorganic to organic phosphorus. Furthermore, the synthesized pyrrole-functionalized phosphorodithioates demonstrate potent antibacterial properties against Staphylococcus aureus.

The production of chemicals using carbon dioxide (CO₂) as the one-carbon source is a sustainable strategy for organic synthesis. Herein, we report an unprecedented rhodium-catalyzed, carboxyl-directed aryl C−H carboxylation of benzoic acids with CO₂ under redox-neutral conditions to afford valuable phthalic acids. In addition, this method could be modified for benzamides by using a different N-heterocyclic carbene ligand to produce phthalimides, demonstrating the versatility of this protocol.

Pseudomonas aeruginosa is an opportunistic pathogen responsible for cystic fibrosis, bloodstream infections and hospital-acquired pneumonia. The O-antigen of lipopolysaccharide on the cell surface of P. aeruginosa has been identified as a promising target for the development of carbohydrate-based vaccines. In this study, we present the first total synthesis of the tetrasaccharide repeating unit of P. aeruginosa serotype 4 O-antigen using a linear [((1+1)+1)+1] glycosylation strategy. All rare amino sugars were synthesized from commercially available monosaccharides. The formation of 1,2-cis L-fucosamine glycosidic bonds was achieved with high efficiency and stereoselectivity by judicious choice of C3/C4-OH protecting groups of L-fucosamine. The N-phenyl trifluoroacetimidate glycosyl donors have proven to be more efficient than selenoglycoside or thioglycoside donors during glycosylation, particularly when coupling with the low-reactivity C3-OH group of the O4-Bz protected L-FucN₃ acceptor. TBSOTf has demonstrated higher efficacy as a catalyst compared to TMSOTf for promoting glycosylation with less reactive acceptors. The synthetic tetrasaccharide repeating unit of P. aeruginosa serotype 4 O-antigen, which incorporates a pentyl amine linker at the reducing end, has been prepared for conjugation with carrier proteins or for utilization in microarray studies aimed at further immunological investigations.

Herein, we developed a tertiary amine-catalyzed stereoretentive multi-component cascade reaction featuring an amidation/[4 + 1] annulation/decarboxylation/Curtius rearrangement/[2 + n] annulation sequence. This metal-free and step-economic method provided a broad range of cyclic ureas/urethanes in green solvent under mild conditions without employing explosive and toxic reagents. Importantly, this reaction generated isocyanates in situ under catalytic conditions via a decarboxylation/Curtius rearrangement process of dioxazolones.

1-Indenones commonly occur in many bioactive and material molecules, thus their highly efficient synthesis attracts much attention from the synthetic community. In this manuscript, we reported an efficient method for their preparation. This reaction used the ortho-vinyl carboxylic acids as the starting material and took place through the intramolecular vinyl C–H acylation with carboxyl group. By the strategy, a wide range of 1-indenones, including both 3-substituted and 2,3-disubstituted ones, were precisely synthesized in high yields. Moreover, this reaction featured a high functional group tolerance. In addition, this reaction could be scaled up without any decrease in the reaction efficiency. We anticipate this new reaction will find wide applications in organic synthesis.

Aminosilylalkanes are important motifs in bioactive molecules, yet methods for their direct incorporation remain limited. In particular, the efficient introduction of gem-difluoro groups–known to significantly modulate the physical, chemical, and biological properties of organic molecules–into aminosilylalkane remains a challenge. Herein, we report a cobalt-catalyzed silyldifluoromethylamination of styrenes using TMSCF₂H and nitrogen nucleophiles. By employing readily available starting materials, a series of complex, highly functionalized aminosilyldifluoroalkane derivatives were synthesized in moderate to good yields. This methodology establishes a novel strategy for constructing organosilicon compounds, complementing existing synthetic approaches.

Asymmetric cascade Heck/C–H functionalization has emerged as an appealing strategy for activating inert C–H bonds and conveniently synthesizing heterocycles with quaternary centers, owing to the domino sequence of carbopalladation followed by C–H functionalization enabling efficient construction of multiple bonds in one pot. Herein, a palladium-catalyzed enantioselective cascade Heck/intermolecular direct heteroarylation reaction of unactivated alkenes with heteroarenes is developed, providing a facile access to diverse bis-heterocycles of great practicality bearing an all-carbon quaternary stereocenter with excellent levels of yields and enantioselectivities under mild conditions. Moreover, the synthetic utility of this strategy is further demonstrated by the versatile transformations of product.

Herein, we report an unprecedented molecular editing strategy for cycloketones that involves the precise translocation and removal of single oxygen atom enabled by dual photoexcited palladium and photoredox catalysis. In contrast to conventional ketone molecular editing strategies, which often rely on the loss of pre-functionalized groups or the addition of additional acylating agents, this approach facilitates the efficient recycling of pre-functionalized moieties. This is accomplished through a photoexcited palladium catalyzed N–O bond cleavage of cycloketone oxime esters, generating cyanoalkyl radicals and a palladium carboxylate complex. The subsequent photoredox-catalyzed deoxygenation, mediated by phosphoranyl radicals, then leads to the coupling of cyanoalkyl radicals, ultimately yielding the desired products. This molecular editing strategy features good atom economy due to precise skeletal modifications, broad compatibility with various functional groups, and significant potential for late-stage functionalization of pharmaceutical derivatives.

The site-selective C–H thiocyanation of quinoline has potential application value but remains undeveloped. We report herein an electrochemical C3-thiocyanation of quinoline derivatives under external oxidant-free conditions. The key to success for this reaction is the in situ formation of activated silylquinolinium salts. This method exhibits mild reaction conditions, broad substrate scope, and excellent site-selectivity. The practicality of this protocol is further demonstrated by a scale-up reaction, follow-up transformations, and late-stage thiocyanation of quinoline-based bioactive molecules.

Achieving high-performance perovskite solar modules (pero-SMs) over large areas under ambient conditions remains a significant barrier to the commercialization of perovskite photovoltaics. This challenge arises from the strong solvent-perovskite coordination interactions in the hygroscopic perovskite precursor ink, which complicate the control of nucleation-growth kinetics and phase evolution during film formation in the presence of moisture, thereby hindering the formation of high-quality perovskite films. In this work, a “guest-solvent” additive strategy was developed by incorporating N,N-dimethylthioformamide (DMT) into the perovskite precursor ink to effectively modulate the coordination between the solvent and perovskite. It is demonstrated that DMT, structurally similar to the “main-solvent” system (DMF and DMSO), possesses lower coordination ability with Pb²⁺ and forms non-covalent interactions with the primary solvents. These interactions weaken the solvent-perovskite coordination without sacrificing solubility, thereby stabilizing homogeneous nucleation and promoting direct crystallization from the sol-gel phase to α-FAPbI₃. As a result, the ambient-printed FAPbI₃ films exhibited high quality, with more compact grain stacking, smoother morphology, higher phase purity, and fewer defects. Consequently, the resulting perovskite solar cells (0.062 cm²) and pero-SMs (15.64 cm²) fabricated via blade coating under ambient conditions achieved remarkable power conversion efficiencies (PCEs) of 24.46% and 22.54%, respectively.

P-chiral organophosphorus compounds have demonstrated unparalleled application potential in diverse fields, including medicine, agricultural science, material science, and life science. Furthermore, they serve as highly effective chiral ligands in both transition metal-catalyzed and organocatalytic asymmetric transformations. In recent years, significant advances have been made in the catalytic asymmetric synthesis of P-chiral organophosphorus compounds, with asymmetric phosphination and hydrophosphination reactions emerging as the dominant strategies. This review systematically summarizes the methodological developments from 2020 to present for constructing P-chiral organophosphorus compounds. The discussion is organized according to different transition metals, aiming to provide a valuable reference and inspiration for researchers in organic synthesis and organophosphorus chemistry.

DNA nanostructures, with their high structural programmability and excellent biocompatibility, have shown tremendous potential in biomedicine applications. This review provides an overview of the self-assembly principles underlying DNA nanostructures, with a particular focus on the current techniques for intracellular tracking, highlighting their advantages and limitations. Building on this foundation, the intracellular behaviors and fates of DNA nanostructures are discussed, along with their potential applications in biomedicine. Finally, future research directions are proposed, offering insights and guidance for the continued development of DNA nanostructures in biomedical fields.