Insertion Reactions Research Articles

Unraveling Dual Mechanisms in Quasi‐Layered Bi2O2Se via Defect Modulation for High‐Performance Aqueous Zn‐Ion Batteries

AbstractDeveloping cathode materials for aqueous zinc‐ion batteries (ZIBs) that offer high capacity, rapid charge–discharge rates, and prolonged cycle life remains a significant challenge. This study explores the use of zipper‐type Bi2O2Se nanoplates modified by selenium vacancy (Vse) modulation, which reduces electron scattering, enhances carrier mobility in [Bi2O2] conducting channels, and decreases coulombic interactions within electrostatic layers. The introduction of Se vacancies facilitates electron transfer from the host to [Bi2O2] channels and reduces scattering in the [Bi2O2] framework, thus improving carrier mobility. These Se‐poor Bi2O2Se nanoplates demonstrate a greater affinity for zinc ions, reduced diffusion barriers, and faster transport kinetics, which enable more efficient Zn‐ion insertion, tripling the electrochemical capacity, improving rate capabilities, and extending cycling life. Enhancements such as reinforced structural integrity and expanded interlayer spaces support a dual Zn‐ion‐driven mechanism involving both insertion and conversion reactions, essential for superior electrochemical storage performance. The results include an impressive discharge/charge capacity of 380.3 mA h g−1 at 0.1 A g−1, a cycle life of up to 10 000 cycles at 5 A g−1, and a current tolerance exceeding 10 A g−1. This research highlights how nano‐ and defect engineering of Bi2O2Se can significantly enhance ionic conductivity, expedite electron transfer, and improve Zn‐ion diffusion.

Advancing carbohydrate functionality: The role of hypervalent iodine

Hypervalent iodine reagents have undergone significant development and widespread application in the functionalization of carbohydrates. This is primarily attributed to their exceptional properties, including mildness, ease of handling, high selectivity, environmental friendliness, and stability. This review aims to emphasize the utilization of hypervalent iodine compounds in the functionalization of carbohydrates. The present article covers various aspects, including glycal functionalization, C–H or N–H insertion reactions, O-arylations, C-2 deoxy-2-iodo glycoconjugates, iminosugars, and C3-oxo-glycals, achieved through the use of hypervalent iodine reagents/catalysts. Additionally, it explores hypervalent iodine-mediated bioactive 1,3,5-trioxocane synthesis followed by rare sugars synthesis.

Design and Synthesis of C₄-Symmetric Axially Chiral β-Aryl Porphyrins and Application for Supporting Ir(III)-Catalyzed Enantioselective C-H Alkylation.

A hitherto unknown class of C4-symmetric Caryl-Cβ (C3, C8, C13, C18) axially chiral porphyrins has been synthesized and the application of their iridium (Ir) complexes in catalytic asymmetric C(sp3)-H functionalization is documented. Cyclotetramerization of enantioenriched axially chiral 2-hydroxymethyl-3-naphthyl pyrroles under mild acidic conditions affords, after oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), the C4-symmetric α,α,α,α-atropenantiomer as an only isolable diastereomer. Both regioisomeric Ir(Por*)(CO)(Cl) complexes catalyze the carbene C-H insertion reaction affording the same enantiomer, albeit with slight difference in enantioselectivity. With the optimum Ir-complex 3e, the 2-substituted arylacetic acid derivatives were generated from diazo compounds and cyclohexadiene in excellent yields and enantioselectivities.

Design and Synthesis of C4‐Symmetric Axially Chiral β‐Aryl Porphyrins and Application for Supporting Ir(III)‐Catalyzed Enantioselective C−H Alkylation

AbstractA hitherto unknown class of C4‐symmetric Caryl−Cβ (C3, C8, C13, C18) axially chiral porphyrins has been synthesized and the application of their iridium (Ir) complexes in catalytic asymmetric C(sp3)−H functionalization is documented. Cyclotetramerization of enantioenriched axially chiral 2‐hydroxymethyl‐3‐naphthyl pyrroles under mild acidic conditions affords, after oxidation with 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ), the C4‐symmetric α,α,α,α‐atropenantiomer as an only isolable diastereomer. Both regioisomeric Ir(Por*)(CO)(Cl) complexes catalyze the carbene C−H insertion reaction affording the same enantiomer, albeit with slight difference in enantioselectivity. With the optimum Ir‐complex 3 e, the 2‐substituted arylacetic acid derivatives were generated from diazo compounds and cyclohexadiene in excellent yields and enantioselectivities.

Nitridation of diamond(111) surface by density functional theory.

Density functional theory was employed to examine the adsorption and thermal evolution of nitrogen species on diamond(111) impacted by microwave N2 plasma. On bare domains of diamond, as represented by the models of C(111)-2 × 1 and graphite-like C(111), N2(ad) is identified as the major surface species; the desorption of N2(ad) proceeds on both models via a concerted process of breaking two C-N bonds. By contrast, there is evidence of the formation of (NH)2(ad) via the insertion reaction of microwave N2 plasma on hydrogenated domains of diamond, as represented by the models of C(111)-2 × 1-H and C(111)-1 × 1-H. Interestingly, contrasting dynamics of desorption of (NH)2(ad) are presented on these two models, that is, via sequential breaking of two C-N bonds on C(111)-2 × 1-H and via concerted breaking of both C-N bonds on C(111)-1 × 1-H. Our results demonstrate that the observed diversity of surface nitrogen species in composition, bonding, vibration, and desorption in prior experiments is linked to domains of a variety of surface terminations and reconstructions on diamond(111).

Enantioselective synthesis of chiral amides by carbene insertion into amide N–H bond

Chiral amides are important structure in many natural products and pharmaceuticals, yet their efficient synthesis from simple amide feedstock remains challenge due to its weak Lewis basicity. Herein, we describe our study of the enantioselective synthesis of chiral amides by N-alkylation of primary amides taking advantage of an achiral rhodium and chiral squaramide co-catalyzed carbene N–H insertion reaction. This method features mild condition, rapid reaction rate (in all cases 1 min) and a wide substrate scope with high yield and excellent enantioselectivity. Further product transformations show the synthetic potential of this reaction. Mechanistic studies reveal that the non-covalent interactions between the catalyst and reaction intermediate play a critical role in enantiocontrol.

Lithium insertion/extraction mechanism in Mg2Sn anode for lithium-ion batteries

Due to its high capacity and excellent voltage properties, the Mg2Sn intermetallic phase is considered a promising anode material for next-generation lithium-ion batteries. However, the rapid capacity loss with cycling presently limits the application of Mg2Sn-based anodes. In this work, the Mg2Sn intermetallic phase was synthesized via a conventional casting method, and mechanisms of lithium ions intercalation into Mg2Sn alloy anodes were systematically studied. Density functional theory (DFT) calculations and electrochemical analyses identified two pathways involving four electrochemical reactions for Li+ intercalation/extraction in the Mg2Sn phase. The first pathway involves the insertion reaction of lithium ions into the octahedral sites of the Mg2Sn face center cubic (FCC) matrix, whilst the second involves the substitution of Mg by Li ions (releasing Mg metal). Furthermore, ex-situ EIS analysis and DFT calculations verified that adjusting the cut-off voltage range could control the reaction pathways. Excessively high or low cut-off voltages adversely impact the stability of the Mg2Sn anode. At cut-off voltages between 0.1 and 1 V, Mg2Sn anodes show very good capacity retention (78 % after 50 cycles), benefiting from the minimized formation of metallic Mg and Sn phases.

High-capacity bismuth phosphate anode with reversible conversion reaction for acid batteries

Acid batteries have emerged as a promising technology in electrochemical energy storage owing to their fast kinetics, cost-effectiveness, and exceptional safety. Most reported acid battery electrodes achieve the electrochemical processes via insertion reactions. However, the strong electrostatic interaction between the proton and the host lattices, as well as the limitations imposed by the crystal structure, leads to most reported electrode materials exhibiting a low specific capacity. Herein, we proposed a reversible conversion-type BiPO4 electrode to avoid strong electrostatic interactions between ions and host lattices and to achieve high specific capacity via high valence-state conversion of Bi3+/Bi in acid batteries. Unlike traditional intercalation-type acid electrode materials, the conversion-type BiPO4 electrode presents potential as a high-capacity electrode material. Due to the high valence-state conversion of Bi3+/Bi, it showcases a high specific capacity of 246 mAh g−1, surpassing most reported electrode materials for acid batteries. Also, the BiPO4 electrode demonstrates excellent reversibility due to the insolubility of BiPO4 and the concentrated PO43- promoting the conversion of Bi3+ in the phosphate electrolyte. Based on the above, the full battery maintained over 600 cycles, displaying the adaptability in acid batteries. This work provides new inspiration for the development of novel electrode materials with high capacity and stability in acid batteries

Generating High-Precision Force Fields for Molecular Dynamics Simulations to Study Chemical Reaction Mechanisms Using Molecular Configuration Transformer.

Theoretical studies on chemical reaction mechanisms have been crucial in organic chemistry. Traditionally, calculating the manually constructed molecular conformations of transition states for chemical reactions using quantum chemical calculations is the most commonly used method. However, this way is heavily dependent on individual experience and chemical intuition. In our previous study, we proposed a research paradigm that used enhanced sampling in molecular dynamics simulations to study chemical reactions. This approach can directly simulate the entire process of a chemical reaction. However, the computational speed limited the use of high-precision potential energy functions for simulations. To address this issue, we presented a scheme for training high-precision force fields for molecular modeling using a previously developed graph-neural-network-based molecular model, molecular configuration transformer. This potential energy function allowed for highly accurate simulations at a low computational cost, leading to more precise calculations of the mechanism of chemical reactions. We applied this approach to study a Claisen rearrangement reaction and a carbonyl insertion reaction catalyzed by manganese.

Oxygen Vacancies Boosted Hydronium Intercalation: A Paradigm Shift in Aluminum‐Based Batteries

AbstractIn aqueous aluminum‐ion batteries (AAIBs), the insertion/extraction chemistry of Al3+ often leads to poor kinetics, whereas the rapid diffusion kinetics of hydronium ions (H3O+) may offer the solution. However, the presence of considerable Al3+ in the electrolyte hinders the insertion reaction of H3O+. Herein, we report how oxygen‐deficient α‐MoO3 nanosheets unlock selective H3O+ insertion in a mild aluminum‐ion electrolyte. The abundant oxygen defects impede the insertion of Al3+ due to excessively strong adsorption, while allowing H3O+ to be inserted/diffused through the Grotthuss proton conduction mechanism. This research advances our understanding of the mechanism behind selective H3O+ insertion in mild electrolytes.

Oxygen Vacancies Boosted Hydronium Intercalation: A Paradigm Shift in Aluminum-Based Batteries.

In aqueous aluminum-ion batteries (AAIBs), the insertion/extraction chemistry of Al3+ often leads to poor kinetics, whereas the rapid diffusion kinetics of hydronium ions (H3O+) may offer the solution. However, the presence of considerable Al3+ in the electrolyte hinders the insertion reaction of H3O+. Herein, we report how oxygen-deficient α-MoO3 nanosheets unlock selective H3O+ insertion in a mild aluminum-ion electrolyte. The abundant oxygen defects impede the insertion of Al3+ due to excessively strong adsorption, while allowing H3O+ to be inserted/diffused through the Grotthuss proton conduction mechanism. This research advances our understanding of the mechanism behind selective H3O+ insertion in mild electrolytes.

Iron(II) Phthalocyanine-Catalyzed Homodimerization and Tandem Diamination of Diazo Compounds with Primary Amines: Access to Construct Substituted 2,3-Diaminosuccinonitriles in One-Pot.

We herein first report the homodimerization and tandem diamination of diazo compounds with primary amines catalyzed by the iron(II) phthalocyanine (PcFe(II)), which can construct one C-C bond and two C-N bonds within 20 min in one-pot. Compared to the traditional metal-catalyzed N-H insertion reaction between amines with diazo reagents, the developed reaction almost does not generate the N-H insertion product, but the homodimerization/tandem diamination product. The proposed mechanism studies indicate that primary amines play a crucial role in the homocoupling of diazo compounds via dimerization of iron(III)-acetonitrile radical generated from the reaction between diazoacetonitrile with PcFe(II) coordinated by bis(amines); the β-hydride elimination is involved, and then, the attack of primary amines toward the carbon atoms on the formed C-C bond is followed. Moreover, this novel reaction can be used to effectively prepare substituted 2,3-diaminosuccinonitriles with high yields and even up to >99:1 d.r., encouragingly these products contain both 1,2-diamines and succinonitrile motifs, which are two classes of important organic compounds with significant applications in many yields. This reaction is also suitable for the gram-scale preparation of 2,3-bis(phenylamino)succinonitrile (2a) with a yield of 84%. Therefore, the developed reaction represents a new type of transformation.

A Mild Metal‐Free Approach for the Direct Synthesis of Carbamoyl Azides from Carboxylic Acid Redox Active Esters

AbstractCarbamoyl azide is a pivotal compound used in the transformation into urea and amines, as well as in nitrene insertion reactions. In this study, we present a pioneering method for synthesizing carbamoyl azide directly from acid redox active esters without the use of metals or oxidants. This approach demonstrates tolerance for various functional groups, enhancing its applicability. Furthermore, this technique facilitates late‐stage modifications of natural products and pharmaceuticals, thereby accelerating the development and identification of novel drug candidates.

Upcycling of waste polycarbonate to recyclable Poly(carbonate-imines) with exceptional thermal properties and unprecedented flame retardancy

This study introduces an innovative method for upcycling waste polycarbonate (WPC) into poly(carbonate-imines) (PCIs), which exhibit exceptional thermal properties and unprecedented flame retardancy. Utilizing a novel insertion reaction of 2-((4-nitrophenoxy)methyl)oxirane with WPC, followed by hydrogenation, we have synthesized WPC-derived amine (WPC-NH2). This amine is further reacted with bifunctional aldehydes to form PCIs that not only meet vitrimer criteria (characterized by stress relaxation and thermal reprocessability through imine metathesis) but also demonstrate superior thermal stability (Tg up to 228 °C) and low thermal expansion (42 ppm/°C). Importantly, these PCIs achieve a UL-94 V-0 rating and exhibit significantly reduced total heat release (11.8 KJ/g), positioning them as prime candidates for sustainable, high-performance materials. The synthesis process supports recycling, showcasing a practical approach to the degradation of PCI-based CFRPs and recovery of intact carbon fibers, underscoring the environmental benefits of this method.

Generation and Identification of the Trifluorosilylarsinidene F3SiAs and Isomeric Perfluorinated Arsasilene FAsSiF2.

The trifluorosilylarsinidene F3SiAs in the triplet ground state has been generated through the reaction of laser-ablated silicon atoms with AsF3 in cryogenic Ne- and Ar-matrices. The reactions proceed with the initial formation of perfluorinated arsasilene FAsSiF2 in the singlet ground state by two As-F bonds insertion reaction on annealing. The trifluorosilylarsinidene F3SiAs was formed via F-migration reactions of FAsSiF2 under irradiation at UV light (λ = 275 nm). The characterization of FAsSiF2 and F3SiAs by IR matrix-isolation spectroscopy is supported by computations at CCSD(T)-F12/aug-cc-pVTZ and B3LYP/aug-cc-pVTZ levels of theory.

Enantioselective Access to β-Amino Carbonyls via Ni-Catalyzed Formal Olefin Hydroamidation.

We herein describe a Ni-catalyzed formal hydroamidation of readily available α,β-unsaturated carbonyl compounds to afford valuable chiral β-amino acid derivatives (up to >99:1 e.r.) using dioxazolones as a robust amino source. A wide range of alkyl-substituted olefins conjugated to esters, amides, thioesters, and ketones were successfully amidated at the β-position with excellent enantioselectivity for the first time. Combined experimental and computational mechanistic studies supported our working hypothesis that this unconventional β-amidation of unsaturated carbonyl substrates can be attributed to the polar-matched migratory olefin insertion of an (amido)(Cl)NiII intermediate, in situ generated from the dioxazolone precursor.

Specific, nondestructive, and durable adhesion primer for polyolefins

Gluing polyolefins [e.g., polyethylene (PE) and polypropylene (PP)] results in a very challenging task. The main reason relies on their low surface energy, which reduces the affinity between the polyolefin surface and the chosen adhesive. To tackle this problem, the most commonly used solutions are physical surface treatments, such as plasma, corona, and flame, which introduce hydrophilic moieties on the plastics surface, thus increasing their surface energy. These approaches require special setups, are unspecific, and can induce material degradation. Furthermore, they provide a transient solution, making the storage of pretreated substrates not recommended. In this work, we developed an easy-to-apply primer for durable bonding of adhesives on PE and PP, as robust alternative to physical treatments. Our primer contains a surface-anchoring moiety and an adhesive-binding group to covalently react with the polyolefin substrate and with the glue. As a surface-anchoring moiety, we chose the perfluorophenylazide (PFPA), which is known to undergo a C–H insertion reaction upon UV activation, while as adhesive-binding groups, we selected OH functions, which can covalently react with the most common commercially available glues. When these two features (i.e., PFPA and OH) are combined in a single molecule, the reaction with the substrate does not occur and the molecule is only physisorbed, inducing no adhesion improvement. Chemisorption only occurs with bicomponent formulations, comprising a hydrophobic trifunctional PFPA and a polymer bearing OH and PFPA groups. Those induced improved adhesion on PP compared to the golden standard plasma with polyurethane-based and two-component epoxy adhesives. Storing the coated substrates at room temperature for up to two months did not alter the adhesion performance, thus further ascribing the developed primers as a promising alternative to plasma treatment.

Heterogeneous Fe-N-C Catalyst for Aerobic Dehydrogenation of Hydrazones to Diazo Compounds Used for Carbene Transfer.

Organic diazo compounds are versatile reagents in chemical synthesis and would benefit from improved synthetic accessibility, especially for larger scale applications. Here, we report a mild method for the synthesis of diazo compounds from hydrazones using a heterogeneous Fe-N-C catalyst, which has Fe ions dispersed within a graphitic nitrogen-doped carbon support. The reactions proceed readily at room temperature using O2 (1 atm) as the oxidant. Aryl diazoesters, ketones, and amides are accessible, in addition to less stable diaryl diazo compounds. Initial-rate data show that the Fe-N-C catalyst achieves faster rates than a heterogeneous Pt/C catalyst. The oxidative dehydrogenation of hydrazones may be performed in tandem with Rh-catalyzed enantioselective C-H insertion and cyclopropanation of alkenes, without requiring isolation of the diazo intermediate. This sequence is showcased by using a flow reactor for continuous synthesis of diazo compounds.

Three Birds with One Sulfur: Construction of Sulfur-Bridged Porous Organic Polymers for Efficient Gold Adsorption.

Sulfur is a massive byproduct of the petrochemicals industry and hardly employed as a building block for porous organic polymers (POPs). Here, a new family of sulfur-bridged POPs has been prepared via a C-H insertion reaction between sulfur and polycyclic aromatic hydrocarbons. Sulfur works as a solvent, external cross-linker, and porogen simultaneously during the polymerization process. The products demonstrate high porosity and maximum surface area of 1050 m2 g-1 with abundant accessible active sites, contributing to the nanometerization of sulfur and significantly enhancing the inherent affinity between heteroatoms toward soft metal ions. Therefore, they exhibit a high absorption capacity for Au(III) of 3287 mg g-1 and excellent absorption selectivity and removal efficiency via a performance evaluation even in real electronic wastewater. This synthetic strategy to prepare high added-value functional POPs with sulfur not only sheds light on designing high-performance gold adsorption materials and emerging POPs, but also promotes a sustainable development protocol.

Synthesis of Novel Polymers with Biodegradability by Main-Chain Editing of Chiral Polyketones.

Although the use of biodegradable plastics is suitable for unrecoverable, single-use plastic, their high production cost and much lower variety compared to commodity plastics limit their application. In this study, we developed a new polymer with potential biodegradability, poly(ketone/ester), synthesized from propylene and carbon monoxide. Propylene and carbon monoxide are easily available at low costs from fossil resources, and they can also be derived from biomass. Using an atom insertion reaction to the main chain of the polymer, the main-chain editing of the polymer molecule proceeded with up to 89% selectivity for atom insertion over main-chain cleavage.