Direct Synthesis Research Articles

Direct Asymmetric Synthesis of α‐Aminoimines from 1,2‐Bis‐N‐Sulfinylimines by Using Allyl Boronic Acids

AbstractA unique direct asymmetric synthesis of α‐aminoimines is realized, through rapid and exclusive mono‐allylation of chiral bis‐N‐sulfinylimines using allylboronic acids. The highly selective allylation was possible as electrophilic imine functional group in the product α‐aminoimines remained unreactive towards allyl boronic acid nucleophiles. Notably, by varying the geometry and chiral auxiliary, all four isomers of the α‐aminoimines were accessed from readily available precursors. A range of allyl nucleophiles, which are tricky to generate by other means possessing highly reactive functional groups also took part in this reaction, expanding the scope further. The applicability of the products α‐aminoimines were further demonstrated by accessing a range of structurally diverse chiral cyclic and acyclic 1,2‐diamines bearing adjacent stereocenters through addition of a second nucleophile or Prins‐type cyclization by exploiting the nucleophilicity of the tethered alkene moiety. Moreover, the leaving group aptitude of sulfinyl auxiliary attached to imine, was exploited to access valuable chiral α‐aminonitriles under thermal conditions without employing any reagents. Detailed DFT calculation revealed a chair‐like transition state, arising from corresponding allylboroxine species, likely operating for the allylboration reaction across imine.

Direct Synthesis of Perovskite Quantum Dot Photoresist for Direct Photolithography.

Perovskite quantum dots (PQDs) photoresists are promising building blocks for photolithographically patterned devices. However, their complex synthesis and combination processes limit their optical properties and potential patterning applications. Here, we present an exceptionally simple strategy for the synthesis of PQDs photoresist. Unlike traditional approaches that involve centrifugation, separation, and combination processes, our direct synthesis technique using polymerizable acrylic monomer as solvent to fabricate PQDs photoresists without complex post-synthesis process. We demonstrate that the change in solubility of the precursors is the main reason for the formation of PQDs in the polymerizable monomer. By direct photolithography, colorful PQD patterns with high photoluminescence quantum yields and excellent fluorescence uniformity are successfully demonstrated. This work opens a new avenue for the direct synthesis of PQDs photoresist, expanding their applications in various integrated applications, such as photonic, energy harvesting, and optoelectronic devices.

Direct Synthesis of Perovskite Quantum Dot Photoresist for Direct Photolithography

Perovskite quantum dots (PQDs) photoresists are promising building blocks for photolithographically patterned devices. However, their complex synthesis and combination processes limit their optical properties and potential patterning applications. Here, we present an exceptionally simple strategy for the synthesis of PQDs photoresist. Unlike traditional approaches that involve centrifugation, separation, and combination processes, our direct synthesis technique using polymerizable acrylic monomer as solvent to fabricate PQDs photoresists without complex post‐synthesis process. We demonstrate that the change in solubility of the precursors is the main reason for the formation of PQDs in the polymerizable monomer. By direct photolithography, colorful PQD patterns with high photoluminescence quantum yields and excellent fluorescence uniformity are successfully demonstrated. This work opens a new avenue for the direct synthesis of PQDs photoresist, expanding their applications in various integrated applications, such as photonic, energy harvesting, and optoelectronic devices.

Direct mechanochemical synthesis of nano-LiAlH4 promoted by 0.696 wt% TiCl4 catalyst surface-modified Al powder

LiAlH4, known for its high hydrogen capacity and metastable nature, is a promising hydrogen source under mild conditions. However, its reversible regeneration from stable binary dehydrogenation phases (LiH/Al) is thermodynamically and kinetically hindered. By constructing a homogeneous and highly dispersed molecular layer of TiCl4 on the surface of the Al reactant to enhance the kinetics of the multiphase interfacial reaction, we achieved the direct mechanochemical synthesis of nano-LiAlH4, bypassing the intermediate phase Li3AlH6. Using the strong Lewis acidity of Ti4+, TiCl4 was chemically adsorbed onto the surface of the Al powder through Ti-O-Al bonds, with a loading capacity of only 0.696 wt%. The obtained TiCl4 surface-modified Al powder and LiH were hydrogenated by ball milling for 10 h under hydrogen pressure to synthesize nano-LiAlH4, which was then dehydrogenated at room temperature. This indicates that the crucial effects of the catalytic sites were dispersed on the reactant surface to ensure the local environment of the multiphase absorption/desorption hydrogen reaction interface and promote the reaction kinetics.

Emerging Trends for the Direct Synthesis of Dithiocarbamates

Dithiocarbamates are common structural motifs in various bioactive compounds, attracting considerable attention due to their wide‐ranging applications in organic synthesis, material science, agrochemicals, and the pharmaceutical industry. Given the significant bioactivity and extensive applications of dithiocarbamates, the continuous pursuit of their efficient and diverse synthetic methods remains critical and urgent. Direct dithiocarbamation reactions can introduce ‐S‐C(S)NR2 group directly into parent molecules, providing shorter, greener, and more practical pathways for the synthesis of organodithiocarbamates. This article offers a comprehensive overview of the latest advancements in direct dithiocarbamation reactions, categorizing them based on the different sources of the ‐S‐C(S)NR2 group, with a particular emphasis on elucidating substrate scope and reaction mechanisms. Additionally, some synthetic limitations and applications of these methods are discussed. This review aims to provide the latest advancements in this field to both general readers and professional practitioners, inspiring innovative ideas for the synthesis of organosulfur compounds.

Dual-engine-driven realizing high-yield synthesis of Para-Xylene directly from CO2-containing syngas

The direct synthesis of light aromatics, especially para-xylene (p-X), from syngas/CO2 is drawing strong interest, but improving the space-time yield (STY) of p-X is a significant challenge. Here, a dynamic “dual-engine-driven” (DED) catalytic system is designed by combining two partners of ZnCr and FeMn (named “dual-engine”) with Z5@SiO2 capsule zeolite. The DED catalyst of 1.0%FeMn&[ZnCr&Z5@SiO2] shows an extremely higher p-X STY of 36.1 gp-x·kgcat-1·h-1, about eight times higher than that of [ZnCr&Z5]. DED manipulates ZnCr engine for methanol formation and drives FeMn engine for light olefins generation together, and then the formed methanol and light olefins are coordinately converted in situ into p-X-rich aromatics over Z5@SiO2. The DED model boosts the driving force for syngas/CO2 conversion, simultaneously concerting the cooperation of “dual-engine” for p-X generation, resulting in extremely high STY of p-X. This study achieves non-petroleum p-X production at industrial-relevant level and advances knowledge in designing innovative heterogeneous catalysts.

Ordered versus Non-Ordered Mesoporous CeO2-Based Systems for the Direct Synthesis of Dimethyl Carbonate from CO2.

In this work, non-ordered and ordered CeO2-based catalysts are proposed for CO2 conversion to dimethyl carbonate (DMC). Particularly, non-ordered mesoporous CeO2, consisting of small nanoparticles of about 8 nm, is compared with two highly porous (635-722 m2/g) ordered CeO2@SBA-15 nanocomposites obtained by two different impregnation strategies (a two-solvent impregnation method (TS) and a self-combustion (SC) method), with a final CeO2 loading of 10 wt%. Rietveld analyses on XRD data combined with TEM imaging evidence the influence of the impregnation strategy on the dispersion of the active phase as follows: nanoparticles of 8 nm for the TS composite vs. 3 nm for the SC composite. The catalytic results show comparable activities for the mesoporous ceria and the CeO2@SBA-15_SC nanocomposite, while a lower DMC yield is found for the CeO2@SBA-15_TS nanocomposite. This finding can presumably be ascribed to a partial obstruction of the pores by the CeO2 nanoparticles in the case of the TS composite, leading to a reduced accessibility of the active phase. On the other hand, in the case of the SC composite, where the CeO2 particle size is much lower than the pore size, there is an improved accessibility of the active phase to the molecules of the reactants.

Study on Continuous-Flow Process for Direct Synthesis of p-Aminophenol from Nitrobenzene

Study on Continuous-Flow Process for Direct Synthesis of <i>p</i>-Aminophenol from Nitrobenzene

Direct Synthesis of Sugar Amides by Aerobic One-Pot Oxidative Amidation of Unprotected Carbohydrates

Direct Synthesis of Sugar Amides by Aerobic One-Pot Oxidative Amidation of Unprotected Carbohydrates

Synthesis of Bridged Five-Membered Ring Systems by Type II [3 + 2] Annulation of Allenylsilane-ene.

The first type II intramolecular [3 + 2] annulation of allenylsilane-ene has been achieved, enabling diastereoselective and efficient construction of synthetically challenging bridged five-membered ring systems such as bicyclo[3.2.1]. This mild and direct process shows a broad substrate scope and is highly stereospecific. Particularly, this work represents the first stereoselective method for the direct synthesis of bicyclo[3.2.1] ring systems from acyclic precursors. Additionally, the first asymmetric total syntheses of (+)- and (-)-strepsesquitriol, and the efficient formation of the synthetically challenging tetracyclic core of pierisjaponol D are achieved by this type II [3 + 2] annulation reaction.

Synthesis Route to Single-Walled Zeolite Nanotubes Enabled by Tetrabutylammonium Hydroxide.

Single-walled zeolite nanotubes (ZNT) were recently synthesized in a narrow compositional window. ZNT structural features-thin zeolitic walls and large mesopores-can allow for easy access of small molecules to zeolite micropores, but they also impart processing limitations for these materials, such as challenges with conventional aqueous ion-exchange conditions. Conventional solid- and liquid-phase ion exchange of calcined NaOH-derived ZNT (NaH-ZNT) results in structural degradation to either 2D sheet-like phases, 3D nanocrystals, or amorphous phases, motivating different direct synthesis routes and unconventional ion-exchange procedures of uncalcined ZNT precursors. Here, a modified synthesis route for ZNT synthesis is introduced that facilitates facile ion exchange as well as incorporation of additional non-Al heteroatoms in the zeolite framework. Tetrabutylammonium hydroxide (TBAOH) is used as a hydroxide source and co-OSDA, enabling synthesis of new compositions of ZNT, otherwise unachievable by post-modification of previously reported NaH-ZNT. By varying the gel composition, synthesis temperature, crystallization time, hydroxide source, silicon source, and aluminum source, productive conditions for the new TBAOH synthesis are developed, leading to increased strong acid site density in the ZNT. The collected results demonstrate the sensitivity of the ZNT synthesis to many key parameters and show that the ZNT forms only when Si/(Al + T) ∼ 30 in these synthesis gels and with specific Si and Al sources, and always in the presence of trace Na+. Catalytic testing, via the tandem CO2 hydrogenation to methanol and methanol to aromatics reaction, shows that ZNTs provide adequate catalytic activity (acidity), relative to their conventional 3D counterparts in converting methanol to aromatic compounds.

Direct synthesis of polar functionalized linear low density polyethylene (LLDPE) using slow-chain-walking palladium catalysts

Linear low-density polyethylene (LLDPE) is the most widely produced type of polyethylene resin. In this work, we detailed the synthesis and analysis of two bulky α-diimine Pd(II) complexes. These Pd(II) complexes can efficiently synthesize LLDPE-type polyethylene materials (ρ = 0.91–0.93 g/cm3) through ethylene slow-chain-walking polymerization. More interestingly, benefiting from the cationic bulky Pd(II) complexes, polar-functionalized LLDPEs (ρ = 0.91–0.92 g/cm3) are also produced by copolymerization of ethylene with various polar monomers such as 10-methyl undecanoate, methyl acrylate, 10-undecenoic acid. The copolymerization maintains the slow-chain-walking polymerization feature, resulting in a polar copolymer with a high melting point and low branching density. The results of 13C NMR spectral also reveal that polar groups are mainly located at the end of the branches in polar-functionalized LLDPEs.

Ambient-pressure alkoxycarbonylation for sustainable synthesis of ester

Alkoxycarbonylation reactions are common in the chemical industry, yet process sustainability is limited by the inefficient utilization of CO. In this study, we address this issue and demonstrate that significant improvements can be achieved by adopting a heterogeneously catalyzed process, using a Ru/NbOx catalyst. The Ru/NbOx catalyst enables the direct synthesis of methyl propionate, a key industrial commodity, with over 98% selectivity from CO, ethylene and methanol, without any ligands or acid/base promoters. Under ambient CO pressure, a high CO utilization efficiency (336 mmolestermolCO−1h−1) is achieved. Mechanistic investigations reveal that CO undergoes a methoxycarbonyl (COOCH3) intermediate pathway, attacking the terminal carbon atom of alkene and yielding linear esters. The origins of prevailing linear regioselectivity in esters are revealed. The infrared spectroscopic feature of the key COOCH3 species is observed at 1750 cm−1 (C=O vibration) both experimentally and computationally. The broad substrate applicability of Ru/NbOx catalyst for ester production is demonstrated. This process offers a sustainable and efficient approach with high CO utilization and atom economy for the synthesis of esters.

Direct Multicomponent Synthesis of C3-Arylated Pyrroles under Catalyst-Free Conditions

AbstractAn operationally simple catalyst-free protocol for the direct regiospecific synthesis of C3-arylated/alkenylated pyrroles has been developed. The enamine-intermediate, in situ generated from succinaldehyde and a primary amine, was trapped with activated carbonyls before the Paal–Knorr reaction in a direct multicomponent ‘just-mix’ protocol to furnish pyrroles in good yields. Several C3-substituted N-alkylpyrroles have been prepared under open-flask conditions, avoiding protection-deprotection chemistry.

Synthesis and characterization of mesoporous silicate as core and low generation polyamidoamine dendrimer as shell for delivery of 5-fluorouracil from their nano complex

Modern nanomedicine delivers drugs to malfunctioning cells. Several synthetic processes can change the shape, particle size, polydispersity index, surface area, and porosity of mesoporous silica nanoparticles (MSNs). Polyamidoamine (PAMAM) dendrimers are attractive polymers with circular forms, uniform distribution, well-structured branching, internal cavities, and surface terminal groups. The objective of this study is to deliver 5-fluorouracil (5-FU) as passive targeting to carcinogen cells via MSN-PAMAM-G3 nanoparticles. This study involved the direct and adaptable synthesis of MSN as the core vehicle, together with third-generation PAMAM dendrimers as the vehicle shell, with the goal of delivering the 5-FU in a targeted and controllable manner. Tetraethyl orthosilicate (TEOS) and cetyltrimethylammonium bromide (CTAB) are used as templates to make the center nanoparticle. Methyl acrylate (MA) and ethylenediamine (EDA) are monomers that cause the formation of branches in PAMAM. The obtained particles were fully characterized in terms of particle size, polydispersity index, zeta potential, thermal behavior, morphology, pore diameter, pore volume, and specific surface area. The particle size of MSN-PAMAM-G3s showed around 187.71 ± 3.97 nm, with a polydispersity index of 0.17 ± 0.01 and zeta potential of 32.17 ± 1.30 mV. By reducing the ratio of drug to vehicle from 1 to 0.25, a significant increase in the EE% of 5-FU from 21.36 ± 0.70 to 43.12 ± 0.67 was observed. The release of 5-FU from the vehicle (5-FU@MSN and 5-FU@MSN-PAMAM-G3) was shown to be considerably higher in an acidic medium (pH = 5.5) in comparison to a neutral medium (pH = 7.4) (P-value<0.05). Furthermore, in both acidic and neutral conditions, 5-FU release was sustained from the vehicle rather than the 5-FU solution. Our research revealed that the MSN-PAMAM-G3 nanoparticles effectively regulated the encapsulation and release of 5-FU, providing pH-sensitive and sustained medication delivery. It is asserted that this nanocarrier has the potential to effectively deliver 5-FU to cancer cells.

Efficient cascade reactions involving esterification, hydrogen transfer, and lactonization for biomass conversion using MOF/Metal oxide composites as heterogeneous catalysts

Development of heterogeneous catalysts with both Brønsted and Lewis acid properties has proved to be promising and useful because they offer an efficient way to cascade reactions. In this study, we present the synthesis pathway and efficacy evaluation of new composites which combined by sulfonic acid functional group modified TiO2 and MIL-101, analyzing their structure-performance correlation as heterogeneous catalysts in cascade reactions involving esterification, hydrogen transfer, and lactonization. These composites possess an open porous structure (MOF and porous TiO2), as well as active sites including Lewis acid (unsaturated coordination metal), Lewis base (Ti-OH), and Brønsted acid (-SO3H). The role of these active sites and the synergies between them were investigated through the esterification of levulinic acid and the direct synthesis of γ-valerolactone from levulinic acid and furfural under cascade reactions. The composites exhibit a 100% ethyl levulinate (EL) yield at 120°C for 6 hours, with γ-valerolactone yields reaching up to 94.5% (160 °C, 9 h) and 89.5% (160 °C, 16 h) from levulinic acid and furfural, respectively. This synergistic effect of Lewis acid/base and Brønsted acid ensures efficient esterification. The presence of a sulfonic acid group promotes the lactonization reaction, while the Meerwein-Ponndorf-Verley reduction is facilitated by the dual Cr sites located adjacent to each other in the secondary building unit of MIL-101(Cr). Moreover, the double-porous structure of porous TiO2 and MIL-101(Cr) effectively guarantees the efficient mass transfer of reactants and intermediates, leading to enhanced synergistic effects that promote more efficient reaction conversion.

Frontiers and developments of data augmentation for image: From unlearnable to learnable

Data augmentation is a crucial technique for expanding training datasets, effectively alleviating the overfitting issue that arises from limited training data in deep learning models. This paper takes a fresh perspective and offers a scholarly exploration of image data augmentation, following a logical progression from unlearnable to learnable methods. The paper begins by providing a brief overview of the developmental history of data augmentation. It categorizes data augmentation techniques into unlearnable and learnable based on their “variation” strategies. Furthermore, the paper outlines the fundamental properties of data augmentation, including expansiveness, fidelity, generalizability, and self-adaptability. Subsequently, focusing on unlearnable and learnable data augmentation techniques, the paper further divides them into single-sample and multi-sample, global and local, image domain, and feature domain, categorically reviewing the basic principles and effects of various data augmentation methods based on the differences in the sources, scopes, and content of “variation” attributes. Ultimately, the comparative analysis of diverse data augmentation methodologies in specific tasks is conducted alongside a synthesis and projection of future research directions. By comprehensively analyzing diverse image data augmentation methods from a fresh perspective, this review reveals the intrinsic disparities between unlearnable and learnable data augmentation techniques. It paves the way for scholars to embark on innovative paths in data augmentation.

Sublimation Transformation Synthesis of Dual-Atom Fe Catalysts for Efficient Oxygen Reduction Reaction.

Dual-atom catalysts (DACs) have garnered significant interest due to their remarkable catalytic reactivity. However, achieving atomically precise control in the fabrication of DACs remains a major challenge. Herein, we developed a straightforward and direct sublimation transformation synthesis strategy for dual-atom Fe catalysts (Fe2/NC) by utilizing in situ generated Fe2Cl6(g) dimers from FeCl3(s). The structure of Fe2/NC was investigated by aberration-corrected transmission electron microscopy and X-ray absorption fine structure (XAFS) spectroscopy. As-obtained Fe2/NC, with a Fe-Fe distance of 0.3 nm inherited from Fe2Cl6, displayed superior oxygen reduction performance with a half-wave potential of 0.90 V (vs. RHE), surpassing commercial Pt/C catalysts, Fe single-atom catalyst (Fe1/NC), and its counterpart with a common and shorter Fe-Fe distance of ~0.25 nm (Fe2/NC-S). Density functional theory (DFT) calculations and microkinetic analysis revealed the extended Fe-Fe distance in Fe2/NC is crucial for the O2 adsorption on catalytic sites and facilitating the subsequent protonation process, thereby boosting catalytic performance. This work not only introduces a new approach for fabricating atomically precise DACs, but also offers a deeper understanding of the intermetallic distance effect on dual-site catalysis.

Sublimation Transformation Synthesis of Dual‐Atom Fe Catalysts for Efficient Oxygen Reduction Reaction

Dual‐atom catalysts (DACs) have garnered significant interest due to their remarkable catalytic reactivity. However, achieving atomically precise control in the fabrication of DACs remains a major challenge. Herein, we developed a straightforward and direct sublimation transformation synthesis strategy for dual‐atom Fe catalysts (Fe2/NC) by utilizing in situ generated Fe2Cl6(g) dimers from FeCl3(s). The structure of Fe2/NC was investigated by aberration‐corrected transmission electron microscopy and X‐ray absorption fine structure (XAFS) spectroscopy. As‐obtained Fe2/NC, with a Fe–Fe distance of 0.3 nm inherited from Fe2Cl6, displayed superior oxygen reduction performance with a half‐wave potential of 0.90 V (vs. RHE), surpassing commercial Pt/C catalysts, Fe single‐atom catalyst (Fe1/NC), and its counterpart with a common and shorter Fe–Fe distance of ~0.25 nm (Fe2/NC‐S). Density functional theory (DFT) calculations and microkinetic analysis revealed the extended Fe–Fe distance in Fe2/NC is crucial for the O2 adsorption on catalytic sites and facilitating the subsequent protonation process, thereby boosting catalytic performance. This work not only introduces a new approach for fabricating atomically precise DACs, but also offers a deeper understanding of the intermetallic distance effect on dual‐site catalysis.

Polyesters and Polyester Nano- and Microcarriers for Drug Delivery.

Many therapies require the transport of therapeutic compounds or substances encapsulated in carriers that reduce or, if possible, eliminate their direct contact with healthy tissue and components of the immune system, which may react to them as something foreign and dangerous to the patient's body. To date, inorganic nanoparticles, solid lipids, micelles and micellar aggregates, liposomes, polymeric micelles, and other polymer assemblies were tested as drug carriers. Specifically, using polymers creates a variety of options to prepare nanocarriers tailored to the chosen needs. Among polymers, aliphatic polyesters are a particularly important group. The review discusses controlled synthesis of poly(β-butyrolactone)s, polylactides, polyglycolide, poly(ε-caprolactone), and copolymers containing polymacrolactone units with double bonds suitable for preparation of functionalized nanoparticles. Discussed are syntheses of aliphatic polymers with controlled molar masses ranging from a few thousand to 106 and, in the case of polyesters with chiral centers in the chains, with controlled microstructure. The review presents also a collection of methods useful for the preparation of the drug-loaded nanocarriers: classical, developed and mastered more recently (e.g., nanoprecipitation), and forgotten but still with great potential (by the direct synthesis of the drug-loaded nanoparticles in the process comprising monomer and drug). The article describes also in-vitro and model in-vivo studies for the brain-targeted drugs based on polyester-containing nanocarriers and presents a brief update on the clinical studies and the polyester nanocarrier formulation approved for application in the clinics in South Korea for the treatment of breast, lung, and ovarian cancers.