Covalent metal-organic frameworks (CMOFs) combining the chemistry of metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) have demonstrated promising potential as reticular photocatalysts, owing to their tunable structures, high surface areas, and efficient light absorption, which provide enhanced charge separation and improved catalytic activity. Herein, we report three imine-linked CMOFs constructed by Cu(I) cyclic trinuclear units (CTUs) and organic linkers with tunable conjugated functional groups, such as benzene (JNM-61), naphthalene (JNM-62), or anthracene (JNM-63), via dynamic covalent chemistry. Due to the incorporation of conjugated linkers, the obtained CMOFs exhibited good photocatalytic activity for the cross-dehydrocoupling reaction of N-phenyl-tetrahydroisoquinoline with alkynes. Interestingly, the variation of linker conjugation strongly influences the light absorption, charge separation and reactive oxygen species (ROS) generation of the materials, resulting in significantly controlled photocatalytic efficiency. Notably, JNM-63 with anthracene linkers showed more efficient photocatalytic performance than JNM-61 containing benzene units and JNM-62 containing naphthalene moieties, suggesting the extended conjugation enhanced the oxygen activation and electron transfer during the photocatalytic process. This work presents a simple yet effect approach to optimizing reticular photocatalysts via dynamic covalent chemistry.

A KO^tBu-mediated C2-benzylation of quinoline N-oxides with benzylboronates under mild reaction conditions has been developed. The reaction shows broad scope for both of the quinoline N-oxides and benzylboronates, especially, secondary and tertiary benzylboronates are also compatible with this reaction. DFT calculations indicate that the reaction is promoted by the nucleophilic addition of KO^tBu to boronate rather than the deprotonation of benzylic C−H bond with KO^tBu.

Transition metal-catalyzed cyclopropanation reactions of indoles are generally limited to diazo compounds. Herein, an efficient copper-catalyzed cyclopropanation reaction of indoles with N-propargyl ynamides is demonstrated, allowing for practical and atom-economic construction of valuable cyclopropa[b]indolines in generally moderate to excellent yields under mild reaction conditions. Thus, this reaction constitutes a new way for cyclopropanation of indoles involving vinyl cations generated from diyne cyclization as key intermediates. Moreover, such an asymmetric cyclopropanation of indoles via chiral copper catalysis has also been realized. In addition, the formal C(sp²)–H functionalization of indoles is achieved by a one-pot copper-catalyzed diyne cyclization followed by proton acid-mediated ring-opening of cyclopropanes.

Organic conjugated polymers (CPs) enable solar-driven interfacial evaporation through photothermal conversion, yet remain hindered by narrow solar absorption spectra and suboptimal energy conversion efficiency. Herein, we developed an intramolecular charge transfer strategy via donor-acceptor modulation to enhance solar absorption and photothermal conversion capabilities of D-A type CPs. Theory calculations confirm that regulating donor building blocks with varying electron densities tunes the intramolecular charge-transfer dynamics, thereby facilitating near-infrared spectral absorption and non-radiative relaxation. Consequently, BBT-An powder, featuring the donor with the highest electron density, exhibits broad absorption across full solar spectrum with the highest photothermal conversion efficiency under solar irradiation. Moreover, the evaporation rate of BBT-An evaporator attains a water evaporation rate of 1.65 kg·m⁻²·h⁻¹ with 94.19% of water evaporation efficiency under 1 sun. Even when integrated with a thermoelectric module, the hybrid system maintains a stable open-circuit voltage of 159.3 mV under 1-sun illumination with minimal evaporation loss. This work establishes a molecular design strategy for high-efficiency organic solar-thermal materials, advancing their applicability in photothermal technologies through broadband absorption and enhanced energy conversion.

Presented herein is a novel synthesis of 3-hydroxyfluorenones through the cascade reaction of aryl enaminones with benzyl substituted cyclopropanols. The formation of product is initiated by the introduction of an enone moiety onto aryl enaminone with cyclopropanol as a homoenolate precursor through aryl C−H bond activation, followed by intramolecular enamine Michael addition, enol Michael addition, amine elimination and aromatization-driven oxidative dehydrogenation. To our knowledge, this should be the first example for the specific synthesis of 3-hydroxyfluorenone derivatives via simultaneous formation of both indenone and phenol scaffolds through cascade C−H/C−C/C−N bond activation and three C−C bond formation. In general, this newly developed protocol features easily accessible substrates, synthetically and pharmaceutically valuable products, unique reaction pathway, good compatibility with various functional groups and ready scalability.

In the past decades, diazaphospholene hydrides (DAP-H) have emerged as powerful catalysts for a variety of reductive transformations. However, the radical processes with DAPs as catalysts are extremely rare. Herein, a DAP-catalyzed radical process of aryl halides to access γ-spirolactams through a XAT/1,5-HAT/radical addition/HAT process is presented. This reaction features metal-free conditions and broad functional group tolerance, leading to γ-spirolactams in good yields.

Bridged biaryl atropisomers are widely recognized as a significant structural motif commonly found in bioactive molecules and natural products. Herein, we report an organocatalytic dynamic kinetic resolution (DKR) approach for the synthesis of optically pure biaryl-bridged seven-membered lactones. In the presence of a chiral N-heterocyclic carbene (NHC) catalyst, racemic biaryl-bridged hemiacetals, generated in situ from 2’-formyl-2-biphenyl carboxylic acids, undergo stereoselective coupling with NHC-bound acylazolium intermediates derived from NHC and aldehydes. This transformation delivers seven-membered biaryl-bridged lactone products with very high yields and good to excellent regio- and enantioselectivities.

Here, we report an effective approach to the synthesis of anticoagulant fondaparinux, utilizing orthogonal one-pot [1+2+2] glycosylation, simultaneous O,N-sulfation and global debenzylation at atmospheric pressure as key steps. The synthetic route was achieved through the longest linear sequence of 12 steps with 19% overall yield from a commercially available disaccharide. The present synthetic route remarkably enhances synthetic efficiency and streamlines the purification process, thereby opening up a new avenue for the large-scale synthesis of fondaparinux and relevant heparin fragments.

Herein, organophotoredox-catalyzed annulation of enamines with sulfoxonium ylides to construct pyrrole derivatives is developed under transition-metal-free and mild condition. A broad range of readily accessible substrates are suitable for this protocol, providing a convenient and efficient approach to preparing pyrrole derivatives with satisfying yields. Mechanistically, a photoredox-mediated radical chain mechanistic pathway is proposed for this reaction by a synergistic experimental and computational study. Two key radicals, α-imino and α-carbonyl C-radicals derived from enamines and sulfoxonium ylides, respectively, could be generated via two steps of single-electron transfer in a photoredox catalytic loop. Subsequently, the formed α-carbonyl C-radical may attack the alkenyl moiety of enamines. Next, the formed radical adduct could undergo H-atom transfer with sulfoxonium ylides to regenerate the key α-carbonyl C-radical and thus fulfill the chain propagation process. The afforded adduct intermediate could undergo an intramolecular cyclization followed by dehydration to furnish the desired pyrrole derivatives.

Herein, we present a visible-light-driven carbo-carboxylation of alkenes with CO₂ via catalytic electron donor-acceptor (EDA) complex activation. A variety of oxindole-3-acetic acid and derivatives were generated in moderate to excellent yields from N-arylacrylamides and CO₂. Mechanistic studies revealed the formation of an EDA complex between catalytic thiolate and alkene. Notably, this redox-neutral reaction features mild, transition-metal and photocatalyst-free conditions, good functional group tolerance and broad substrate scope. Furthermore, the facile synthesis of key intermediates in natural products underscores the utility of this methodology.

Herein, we reported a copper-catalyzed stereoselective olefinic β-C(sp²)–H imidation of acyclic enamides employing commercially available N-fluorobenzenesulfonimide (NFSI) as an imidating reagent, which allows for the synthesis of various imidation products with mainly E-selective control. This methodology was featured by being ligand-free, having good efficacy, and exhibiting broad substrate scope for acyclic enamides. Mechanistically, the imidyl radical species might be involved in the reaction.

TAD-indole adducts, serving as stable surrogates for reactive triazolinediones (TADs), are pivotal in bioconjugation and polymer chemistry but remain limited by cumbersome synthesis. Current methods rely on preformed TADs or stoichiometric oxidants, posing practical and environmental challenges. Herein, we report a sustainable catalytic cross-coupling protocol to directly synthesize TAD-indole adducts from indoles and urazoles via Ma's oxidation. This one-step method employs the Fe(NO₃)₃·9H₂O/TEMPO/NaCl system with air as the terminal oxidant, achieving high efficiency (up to 86% yield), broad substrate scope (electron-rich/-deficient indoles/urazoles), and mild conditions. The protocol's practicality is demonstrated through gram-scale synthesis and the preparation of blocked TAD cross-linkers for temperature-controlled polymer networks. By circumventing traditional TAD-handling limitations and eliminating excess oxidants, this strategy establishes a green, scalable platform for advancing TAD chemistry in materials and bioconjugation.

The catalytic hairpin assembly amplification strategy, owing to its designability and high specificity, has been widely used for highly sensitive detection of low-abundance miRNAs. However, uncontrollable valency and distance between the hairpin probes result in low reaction rates and efficiency, often necessitating extended incubation times, thereby limiting their practical applications. In this study, we present a controllable linear DNA nanomotor (CLDN) composed of a pair of interval hybridization-modified hairpin DNA probes (H1 and H2) for the highly sensitive and selective detection of miRNAs. By regulating both reaction time and sequence interval, the length of the DNA scaffold generated by rolling circle amplification can be controlled, thus modulating the assembly valency and distance between the hairpin DNA probes. When target miRNAs sequentially initiate the interval hybridization of H1 and H2, the entire DNA nanomotor is rapidly activated through the simultaneous opening of all self-quenching hairpins (H1). Owing to the acceleration from the confined space and domino-like effect, the signal-to-noise ratio is enhanced by approximately 6.73-fold in comparison to conventional DNA cascade reaction. Additionally, the CLDN demonstrates high selectivity in distinguishing between homogeneous miRNA sequences with a single-base difference. Our CLDNs hold great potential for quantitatively analyzing multiple miRNAs in clinical diagnostics.

The design and synthesis of high-mobility n-type near-amorphous conjugated polymers (NACPs) represent a prominent research focus in organic semiconductors. The diketopyrrolopyrrole (DPP) unit is a widely used building block for constructing high-mobility conjugated polymers. However, DPP-based polymers often exhibit semi-crystalline structures and inherent p-type charge-transport characteristics, which hinder their application in n-type flexible electronic devices. To overcome these challenges, this study employs acceptor modulation and terpolymerization by integrating pyridine-flanked DPP with 3,4-difluorothiophene (2FT) and selenophene (Se) as comonomers. Besides, the incorporation of oligo(ethylene glycol) side chains is strategically designed to enhance polymer solubility and favorably modulate the morphology. Thus, a series of polymers, P2FTx (x = 100–0), are synthesized via Stille polycondensation, enabling systematic investigation of the composition-structure-property relationships. It reveals that optimal Se incorporation minimizes torsional barriers and reduces backbone regularity, inducing a near-amorphous phase with locally ordered domains while maintaining suitable energy levels for efficient electron transport. Notably, P2FT90 achieves the highest electron mobility of 0.47 cm²·V^-1·s^-1, highlighting the efficacy of this compositional engineering approach. This study exemplifies a synergistic approach that combines precise control of backbone regioregularity and energy-level engineering to realize high-performance n-type NACPs.

Septosones B and C are a pair of polycyclic avarane-type meroterpenoids which possess a distinctive spiro[4.5]decane backbone and exhibit promising biological activity. We report here the total synthesis of 1'-epi-septosones B and C through an unusual stereospecific 1,2-alkyl migration of a 6/6-fused dienone tertiary alcohol to a spiro[4.5]enedione scaffold. More importantly, two new compounds were found to exhibit potent anti-cancer activity against Hep G2, MV-4-11, and MOLT-4 cell lines with IC₅₀ values as low as 2.1 μM through bioactivity profiling of the synthetic advanced intermediates.

Herein, we report a substrate-controlled palladium-catalyzed divergent decarboxylative cycloaddition of vinyloxazolidine-2,4-diones with azadienes. The reaction of benzofuran-derived azadienes undergoes a decarboxylative (3+2) cycloaddition process to access spiro[benzofuran-butyrolactam] derivatives in good yields with acceptable diastereoselectivities. In contrast, the reaction of benzothiophene-based azadienes proceeds a decarboxylative (5+4) cycloaddition pathway to give benzothieno[1,2-d]diazonin-5-ones in moderate to high yields. Gram-scale synthesis and further transformations demonstrated the potential synthetic utility of the developed protocol.

γ-Lactam is one of the most prevalent heterocyclic building blocks in organic synthesis and pharmaceutical chemistry. However, the direct use of alkynamides as the synthon for the preparation of structurally diverse γ-lactams has remained much underexplored so far. Herein, we presented the first palladium-catalyzed intermolecular carboamidation of alkenes with alkynamides for constructing polyfunctionalized α-methylene-γ-lactams under aerobic oxidative conditions. More importantly, this protocol features broad substrate scope, good functional group tolerance, and good step- and atom-economy. Remarkably, the synthetic value of this synthetic strategy is further demonstrated by applications in the gram-scale synthesis and the late-stage diversification of pharmaceuticals molecules.

Synthetic immunology merges synthetic biology and immunology, offering a new paradigm to unravel complex immune mechanisms and address major diseases. Unlike traditional ligand display platforms that face inherent limitations, DNA nanotechnology provides unparalleled programmability and nanoscale precision, enabling the fine-tuning of key immune parameters like ligand valence state and spatial distribution, as well as receptor-ligand interaction. This review covers recent advances in DNA nanotechnology for immune modulation, highlighting its role in the programmable design of immune responses. We first outline how DNA-based tools facilitate precise interrogation of immune cell mechanics, including receptor-ligand dynamics, ligand spatial arrangement, and mechanotransduction. We then discuss the applications in immune cell engineering, focusing on receptor reprogramming and surface functionalization, through customizable DNA scaffolds that reconfigure cellular communication. The modular nature of DNA nanotechnology further underpins the development of artificial immune cells, bridging synthetic biology with immunotherapy. In addition, we highlight emerging frontiers such as heterogenous multivalent ligand synergy and DNA-based synthetic cells, poised to expand mechanistic insights and therapeutic innovation. By integrating bottom-up design with top-down cellular interventions, DNA nanotechnology establishes a transformative framework for synthetic immunology, providing innovative solutions to fundamental and clinical challenges in immune regulation.