Asymmetric energy transfer (EnT) photocatalysis faces a critical challenge: the spatial segregation between photosensitizer and substrate imposed by chiral catalysts severely restricts EnT efficiency. The Tan group has recently developed a relay energy transfer strategy based on CETA (Chiral EnT Acid) catalysts, which integrate an energy carrier, a catalytic center, and a stereogenic element into a single scaffold. Applied to the dearomative [4+2] cycloaddition of quinolines with alkenes, the CETA catalyst overcomes the EnT barrier, achieving a threefold improvement in energy transfer efficiency and extending the excited-state lifetime of the substrate via reversible energy storage. This work establishes a new paradigm for asymmetric EnT photocatalysis and offers a blueprint for designing chiral catalysts with enhanced energy-transfer capability.

The borrowing hydrogen coupling of alcohols offers a sustainable pathway for alcohol upgrading, yet remains challenging for heteroaryl substrates due to the plausible catalyst poisoning. A highly efficient three-component coupling of heteroaryl alcohols has been accomplished in the presence of a bis-NHC-Ir catalyst, delivering diverse β-alkylated and β-methylated alcoholic products in up to 99 % yields. The newly developed protocol accommodates a broad range of N-, O-, and S-containing substances, including even two distinct heterocyclic ones. Besides confirming a tandem β-alkylation/β-methylation sequence, mechanistic studies revealed that robust NHC-Ir ligation suppresses the plausible heteroatom-induced catalyst deactivation. Gram-scale synthesis and diverse downstream derivatizations underscore the practicality and synthetic value of this protocol for accessing high-value heterocyclics.

The latest investigation on copper-catalyzed enantioselective coupling of alcohols with tertiary halides has been highlighted, with particular emphasis on a novel catalytic system developed by Liu and co-workers. This copper/anionic catalytic system enables highly efficient and enantioselective O-alkylation and C-alkylation of alcohols with tertiary halides, affording sterically hindered chiral dialkyl ethers and chiral all-carbon quaternary center molecules in high yields and high enantioselectivity. Through rational design of the anionic ligand with sufficient steric bulk to accommodate tertiary radicals, combining with copper catalysis, the system effectively suppresses potential side reactions, overcoming the inherent instability and challenges in stereocontrol of tertiary radical intermediates. This strategy provides an efficient synthetic approach for the coupling of alcohols with tertiary halides.

Methanol, as a low-cost, abundant, and sustainable C1 feedstock, has garnered considerable attention for methylation reactions via the borrowing hydrogen (BH) process. Herein, we designed and synthesized two-dimensional (2D) N-heterocyclic carbene–iridium (NHC–Ir) coordination assemblies, which act as self-supporting solid molecular catalysts and exhibit excellent activity and exclusive chemoselectivity in two methylation reactions, including β-methylation of primary alcohols and selective mono-N-methylation of arylamines. The protocol delivers up to 98% yield with quantitative mono-selectivity and a turnover number (TON) up to 4940 under basic conditions. A wide range of structurally diverse primary alcohols and anilines is well tolerated, highlighting the capability of this methodology for late-stage methylation of pharmaceutical molecules bearing methyl groups. Moreover, the solid catalyst demonstrates exceptional stability and recyclability; no obvious loss in activity and selectivity was observed even after seven consecutive runs.

Skeletal editing via atom insertion, deletion or replacement is pivotal for late-stage diversification, yet existing methods largely rely on highly reactive carbene/nitrene intermediates, especially in intermolecular reactions. Zeng and Li’s team developed a substrate-directed photochemical strategy for precise single-carbon replacement at indole C2. Employing tryptamine’s ethylamine side chain as a molecular robotic arm, the cascade process enables efficient carbon remodeling with broad substrate tolerance. It simplifies quebrachamine synthesis to four steps with 31 % yield, and highlights the robotic arm concept as a versatile guideline for precise skeletal editing with broad synthetic prospects.

Stereocontrolled construction of C(sp3)–C(sp3) bonds remains a critical challenge in organic synthesis, since radical intermediates in conventional alkyl–alkyl crosscoupling readily erase stereochemistry of chiral substrates. Recently, Wu, Weix and co-workers developed a nickel-catalyzed stereoretentive decarbonylative C(sp3)–C(sp3) cross-coupling enabled by a pyrazolyl–pyridine ligand. This mild protocol couples α-chiral secondary carboxylic acids with alkyl halides with complete retention of configuration, tolerating various sensitive functional groups. Mechanistic studies confirm a metallo-Curtius rearrangement pathway, where stereospecific decarbonylation of acylnickel(II) intermediates generates alkylnickel species; stereoselectivity is controlled by the competition between radical capture and reversible β-hydride elimination, excluding radical racemization. The method efficiently converts α-amino and α-hydroxy acids into cyclic and acyclic chiral alkyl–alkyl adducts with high diastereocontrol, and enables facile synthesis of natural product and pharmaceutical intermediates. This work integrates classical rearrangement with nickel catalysis, providing a practical strategy to construct sp3-rich chiral molecules from enantiopure carboxylic acids, and holds great potential for academic and industrial synthetic applications.

ABSTRACT As one of the most important pincer coordination molecules, terpyridine (Tpy) metal complexes have emerged as a vibrant research frontier in coordination chemistry, catalysis and materials science due to their unique chelation versatility and modular structural tunability. In particular, Tpy–Zn complexes exhibit exceptional photochemical and photophysical characteristics, low toxicity, and self‐assembly propensity, making them a novel and versatile platform for functional material design. This review comprehensively summarizes the design strategies of various Tpy–Zn complexes and their corresponding materials, including discrete molecular complexes, supramolecular assemblies (e.g., gels, metal organic frameworks, cages) and their composites, while highlighting their recent advances in three key domains: (1) visual molecular recognition and sensing, (2) stimuli‐responsive smart functional materials, and (3) photocatalytic organic transformations. Additionally, remaining synthetic obstacles, unresolved controversies in structure–property relationships, and future perspectives for the development of novel Tpy–Zn complexes are thoroughly discussed. This review aims to establish a rational design paradigm for next–generation Tpy–Zn–based functional materials, thereby providing in‐depth mechanistic insights and sparking their innovative applications functional materials science.

Photocatalytic efficiency is often inherently constrained by either singlet or triplet excited states of the catalysts. Achieving the synergistic utilization of energy from both excited states to maximize catalytic performance remains a pivotal challenge. Jiang and co-workers proposed a dual-mode strategy to construct donor–acceptor (D–A) covalent organic frameworks (COFs) by incorporating electron-donating porphyrin motifs and electron-accepting benzothiadiazole units. After rational optimization, these COFs exhibited strong D-A pairing, short D-A distances, and hydrogen-bonding interactions, enabling the effective harnessing energy from both singlet and triplet excited states, which resulted in highly efficient photocatalytic performance. Remarkably, the spatially distinct electron and energy transfer facilitated by the well‑defined porous architecture allowed for the catalysis of diverse condensation and coupling reactions with exceptional efficiency and selectivity. Consequently, the rational design of D-A COFs proves to be a powerful approach for not only enhancing catalytic efficiency but also extending their potential application.

ABSTRACT Aliphatic primary amines serve as essential precursors for pharmaceuticals, fine chemicals, and functional materials. However, conventional synthetic methods for these amines typically involve tedious multi‐step processes with suboptimal efficiency and cost‐effectiveness. Direct amination of readily available alcohols to access primary amines is highly appealing but remains challenging. Herein, we report a manganese‐catalyzed transamination of alcohols using commercially available benzylamine as the amination reagent. The protocol demonstrates broad substrate compatibility and excellent selectivity toward aliphatic primary amines even at low catalyst loadings, up to 1.1×10 6 TON could be achieved. Mechanistic studies reveal that bases play crucial roles in achieving excellent selectivity, in which t BuOK facilitates imine intermediate rearrangement and KOH acts as a nucleophile to promote imine bond cleavage, thus enabling the formation of desired primary amines instead of conventional N ‐alkylated secondary amines.

Efficient capture of radioactive iodine species is essential for nuclear accident preparedness and aqueous waste treatment, but remains a challenging task. Herein, a triangle imidazolium cyclophane is readily accessible by Friedel-Crafts reaction from benzimidazole precursor, which behaves as an efficient absorbent to quickly capture iodine vapor and its aqueous solution with a maximum adsorption capacity of 3.54 g g−1, exceeding most known macrocycles. Moreover, after 30 cycles of reuse, the material still maintained an iodine adsorption efficiency of over 84

Cytochromes P450(P450s or CYPs)constitute a largesuperfam-ily of heme-thiolate monooxygenases that are ubiquitous in nature.These remarkable enzymes serve as highly versatile biocatalysts capable of mediating selective oxidations across an exception-ally broad range of organic substrates.In 1979,the pioneering work of Groves and colleagues established the first biomimetic model of P450 enzymes,featuring a synthetic Fe(TPP)Cl catalyst.This landmark system was structurally inspired by the Fe(Ⅲ)-protoporphyrin Ⅸ core that characterizes native P450 enzymes[1].

The bicarbonate-formate (HCO3 - - HCO2 -) interconversion provides a promising cycle for a conveniently accessible hydrogen storage system via reversible dehydrogenation and hydrogenation processes. Existing catalytic systems often use organic solvents, tedious optimization as well as manipulation of pH values, solvent, pressure and various additives. Herein, we present an operational, robust, safe and cost-effective catalytic system for hydrogen storage and liberation. We have established a unique catalytic system with two different solid organometallic assemblies (NHC-Ru and NHC-Ir) that facilitate the reversible transformation between sodium formate and bicarbonate in aqueous solutions collaboratively and efficiently. Notably, the NHC-Ru catalyst is privileged for the hydrogenation of sodium bicarbonate, whereas the NHC-Ir component enables the dehydrogenation of sodium formate, all in a single reaction vessel. What sets this system apart is its simplicity. The H2 discharging and recharging is simply regulated by heating the mixture with or without H2 . Remarkably, this process requires no extra additives or supplementary treatments. Moreover, the reversible hydrogen storage system is durable and can be reused for over 30 cycles without a discernible decline in activity and selectivity. The strategic paradigm in this study shows significant practical potential in hydrogen fuel cell applications. (c) 2025 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

This work focuses on the synthesis and application research of silicon-containing biferrocene derivatives grafted onto hydroxyl-terminated polybutadiene (HTPB), to address the issues of volatility and migration tendency of ferrocene combustion catalysts in solid rocket propellants, as well as the insufficient catalytic performance caused by low iron content in ferrocene-containing polymeric materials. Firstly, a template reaction was employed to optimize the hydrosilylation reaction conditions. In this part, 4-vinyl-1-cyclohexene was employed as substrate, and the ratio of substrate, solvent, reaction time, reaction temperature was optimized. Based on the optimized condition, ferrocene silane derivatives and HTPB were utilized as substrates to obtain HTPB grafted silicon-containing biferrocene compounds. Subsequently, the relationship of biferrocene silane loading and the iron contents as well as the grafting rate were investigated. As the result, three different HTPB grafted silicon-containing biferrocene combustion catalysts were obtained by grafting biferrocene silane derivatives on HTPB polymers through hydrosilylation reactions. The iron contents of above combustion catalysts were 10.7%, 11.9% and 14.1% respectively, which were higher than that of Butacene (8%). At the same time, its thermal stability and catalytic decomposition performance of ammonium perchlorate (AP) were tested. The combustion catalysts were mixed with ultrafine AP at a mass ratio of 5:95, then carefully ground it to uniformity. The solvent was evaporated during the grinding process. After grinding, a mixture of combustion catalyst and AP was obtained, and then differential scanning calorimetry (DSC) and thermogravimetric (TG) study were employed. The results demonstrated that the decomposition temperature of AP under catalytic conditions were reduced. The initial and final decomposition temperatures of AP were reduced after adding 5% biferrocene-containing HTPB, with the final decomposition temperature reduced by about 57 similar to 77 degrees C, and the high decomposition temperature reduced by 87.4 similar to 103.7 degrees C, which could catalyze the decomposition of AP efficiently. These above combustion catalysts might be utilized in HTPB solid rocket propellant in the future.

The direct and selective hydrogen-borrowing transformation of polyols to the corresponding amino alcohols remains a significant challenge. Herein, we demonstrate the selective synthesis of amino alcohols and amino acids from readily available polyols using a tris-NHC-Ir catalyst bearing three N-heterocyclic carbene ligands. Diverse aryl and alkyl amines, as well as vicinal glycols and other biopolyols, are well compatible with good functional group tolerance, achieving up to 93% yields of amino alcohols. Moreover, various amino acids are obtained via subsequent dehydrogenation by using the same catalyst. Mechanistic studies reveal that the low ionization potential of the Ir center within tris-NHC-Ir(III) species is crucial for this selective hydrogen-borrowing process. Our protocol provides an efficient and selective approach for accessing valuable amino alcohols and amino acids from inexpensive biomass-derived alcohols.

The precise synthesis of planar chiral pillar[n]arenes (PAs) faces significant challenges due to their inherent dynamic racemization induced by rapid molecular flipping. To address this issue and enhance conformational stability of these macrocycles, we have developed a strategic approach involving the introduction of sterically bulky aryl (sp(2)) substituents at the molecular rims through dynamic kinetic resolution (DKR). A series of robust and chirality-aligned homo- and hetero-diaryl PAs (n = 5, 6) were achieved with excellent enantioselectivity (>95 % ee) via Pd-catalyzed asymmetric Suzuki-Miyaura coupling reactions. Mechanism study revealed axial steric hindrance, rather than radial substitution, governs conformational chirality-locking in pillar[n]arenes. This work not only provides an attractive protocol for the enantioselective synthesis of planar chiral pillar[n]arenes, but also enriches the library of macrocycles for promising applications in chiral molecular machines, enantioselective sensors, and chiral luminescent materials. (c) 2025 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

Direct conversion of amines to corresponding alcohols is challenging even under harsh reaction conditions. Inspired by enzymatic transamination, we present a transamination borrowing-hydrogen strategy that enables the direct and selective Mn-catalyzed deaminative hydroxylation of benzylamines, affording a broad scope (>30 examples) of alcohols in good yields at low catalyst loadings (down to 0.05 mol%). Notably, methanol serves a dual role as hydrogen donor and amino acceptor, rather than a conventional role as a methylating agent. Mechanistic investigations reveal base plays a pivotal role in facilitating the 1,3-proton transfer process, thereby effectively suppressing N-methylation pathways and favoring alcohol formation.

Aqueous hydroaminomethylation (HAM) of olefins generally requires the use of organic solvents, additives, and high-pressure hydrogen to synthesize amines in satisfactory yields and selectivity. Herein, we accomplish the HAM reactions of long-chain olefins in water without organic solvent or additives by using a hydrophilic bis-NHC-Ir complex as the catalyst. A broad scope of long-chain olefins and amines is well compatible, affording corresponding higher amines in up to 99% yields with excellent linear/branched (l/b) selectivity (up to 94/6). Mechanistic investigations reveal that water acts as both solvent and hydrogen source. The protocol can be readily extended to the synthesis of pharmaceuticals and deuterated analogues with excellent yields and deuterium rates. Moreover, the amine products are easily separated by extraction, and the recovered aqueous phase could be directly used and recycled. This protocol offers a sustainable, safe, and cost-effective approach for synthesizing higher amines.