Multicomponent Coupling Research Articles

Modular Synthesis of Heterobenzylic Amines via Carbonyl Azinylative Amination.

Transformations enabling the synthesis of α-alkyl, α'-2-azinyl amines by addition of 2-heteroaryl-based nucleophiles to in situ-generated and non-activated alkyl-substituted iminium ions are extremely rare. Approaches involving classical 2-azinyl organometallics, such as the corresponding Grignard reagents, often fail to produce the desired products. Here, we report an operationally straightforward solution to this problem through the development of a multicomponent coupling process wherein a soft 2-azinyl indium nucleophile, generated in situ from the corresponding 2-iodo heteroarene and indium powder, adds to an iminium ion that is also formed directly in the reaction. This modular carbonyl azinylative amination (CAzA) displays a broad scope and only a metal reductant is needed to generate a reactive 2-azinyl nucleophile. Beyond the addition to iminium ions, the 2-azinyl addition to polyfluoromethyl ketones forms the corresponding tertiary alcohols. Together, the products of these reactions possess a high degree of functionality, are typically challenging to synthesize by other methods, and contain motifs recognized as privileged in the context of pharmaceuticals and agrochemicals.

Modulation transfer protocol for Rydberg RF receivers

We propose and demonstrate a modulation transfer protocol to increase the detection sensitivity of a Rydberg RF receiver to fields out of resonance from the transition between Rydberg levels. This protocol is based on a phase modulation of the control field used to create the Electromagnetically Induced Transparency signal. The nonlinear wave mixing of the multi-component coupling laser and the probe laser transfers the modulation to the probe laser, which is used for the RF-field detection. The measurements compare well with semi-classical simulations of atom–light interaction and show an improvement in the RF bandwidth of the sensor and an improved sensitivity of the response to weak fields.

Analyzing multicomponent permeation and coupling effects in pervaporation of Acetone-Butanol-Ethanol solutions using Maxwell-Stefan based modeling

The state-of-the-art research in pervaporation lacks a comprehensive understanding of the selective membrane permeation in real and multicomponent mixtures, a factor critical for its widespread commercial adoption. This work elucidates the contribution of various interaction effects, known as coupling phenomena, on the pervaporation of multicomponent Acetone-Butanol-Ethanol (ABE) solutions through a commercial PDMS membrane. Maxwell-Stefan (MS) diffusion formulations, combined with the UNIQUAC thermodynamic model, mostly restricted in literature to binary solutions permeating through a polymer membrane, are extended to multicomponent feed solutions. The thermodynamic correction factor [Γ] and correlation [B]−1 matrices are analyzed to resolve coupling into its thermodynamic and kinetic (diffusive) constituents.A generalized and explicit analytical derivation for calculation of [Γ] by UNIQUAC model is proposed, allowing estimation for any number of permeants. Subsequently, a significant inhibitory coupling of the component fluxes to the driving forces of its accompanying penetrants is revealed. In addition to the non-ideality arising from diagonal elements Γii, the substantial negative off-diagonal elements Γij in the thermodynamic correction matrices anticipate a decline in effective driving forces, butanol fluxes and permeation selectivity as we transition from binary butanol-water to multicomponent ABE mixtures.Following this, a detailed hit-and-trial based strategy is implemented to evaluate the relevance of membrane plasticization, cluster formation and interspecies frictional interactions towards the MS self and cross diffusivities within the [B]−1 matrix. Existing semi-empirical expressions for self-diffusivities in binary alcohol-water systems incorporating plasticization and clustering constants are reformulated and compared for their ability to accurately describe fluxes in binary and ternary ABE solutions. Furthermore, the optimal model fit was found to be insensitive to variation in MS cross-diffusivities. This suggests that the contribution of correlation effects may be neglected altogether, provided the expressions for self-diffusivities are adequately tailored for membrane plasticization and clustering. Notably, while only butanol clustering suffices for binary mixtures, additional aggregates involving butanol-water, water-water, and butanol-acetone/ethanol are suggested to play a crucial role in steering diffusivities in ternary solutions.Consequently, the proposed models exhibit exceptional agreement with experimental data, achieving R2 values of approximately 0.96, 0.95, and 0.98 for butanol flux in binary butanol-water and ternary solutions containing acetone and ethanol, respectively. Besides providing a more cohesive fit to the overall experimental permeation data, the usefulness of this approach lies in significantly simplifying model computations, thus easing the potential modeling of even more complex mixtures.

Modular Synthesis of Heterobenzylic Amines via Carbonyl Azinylative Amination

AbstractTransformations enabling the synthesis of α‐alkyl, α′‐2‐azinyl amines by addition of 2‐heteroaryl‐based nucleophiles to in situ‐generated and non‐activated alkyl‐substituted iminium ions are extremely rare. Approaches involving classical 2‐azinyl organometallics, such as the corresponding Grignard reagents, often fail to produce the desired products. Here, we report an operationally straightforward solution to this problem through the development of a multicomponent coupling process wherein a soft 2‐azinyl indium nucleophile, generated in situ from the corresponding 2‐iodo heteroarene and indium powder, adds to an iminium ion that is also formed directly in the reaction. This modular carbonyl azinylative amination (CAzA) displays a broad scope and only a metal reductant is needed to generate a reactive 2‐azinyl nucleophile. Beyond the addition to iminium ions, the 2‐azinyl addition to polyfluoromethyl ketones forms the corresponding tertiary alcohols. Together, the products of these reactions possess a high degree of functionality, are typically challenging to synthesize by other methods, and contain motifs recognized as privileged in the context of pharmaceuticals and agrochemicals.

Facile synthesis of hierarchical Fe–S co-doped carbon-based composites with superior microwave absorption

Difficulty of multi-component coupling and hierarchical pore structure preparation make it challenging to manufacture highly efficient microwave absorption materials (MAMs). Herein, hierarchical porous carbon composites anchored with various types of iron sulfides are successfully fabricated using a simply feasible heating-induced self-assembly approach. Controllable electromagnetic parameters and impedance matching features of FexSy/AC (amorphous carbon) composites are obtained by varying carbonization temperature. Besides, AC and FexSy provide dielectric and magnetic losses, while defect-rich AC can effectively disperse FexSy nanoparticles, exhibiting high sintering resistance and high-density interfaces, which contributes to polarization losses. Moreover, the unique hierarchical porous structure not only offers better impedance matching, but also enhances microwave loss. The thorough investigation indicates that FexSy/AC nanocomposites exhibit outstanding microwave absorption performance by the joint effect of unique hierarchical porous structure and coupling loss of multi-components. The optimal sample (FSC-700) shows a strongest reflection loss value of up to −78.96 dB with a matching thickness of 2.85 mm, an effective absorption bandwidth (EAB, RL<−10 dB) of 6.98 GHz (11.02–18.0 GHz, spanning Ku-band), and a radar cross section (RCS) reduction value of 21.75 dBm2. In addition, the EAB can reach 13.8 GHz with the simulated thickness varies from 1.0 to 5.5 mm, covering 86 % of the measured frequency range. The in-depth research of the multi-component system with hierarchical porous structure offers an innovative and practical method for high-performance MAMs.

Unexplored catalytic potency of a magnetic CoFe2O4/Ni-BDC MOF composite for the one-pot sustainable synthesis of 5-substituted 1-H tetrazoles

Within the domain of materials science and engineering, significant progress has led to the emergence of innovative materials based on magnetic MOFs, positioning them as promising candidates in the field of catalysis. This research aims to elaborate on the development of a finely tailored magnetic MOF composite; Ni-BDC (Nickel benzene-1,4-dicarboxylate) microflakes which was synthesized through a straightforward in-situ solvothermal approach. Extensive investigations into the structural properties of the resultant hybrid composite were carried out using various characterization techniques encompassing X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET) analysis, atomic absorption spectroscopy (AAS), energy-dispersive X-ray spectroscopy (EDX), thermogravimetric analysis (TGA) and vibrating sample magnetometry (VSM). The developed material demonstrated remarkable efficiency in expediting the synthesis of a diverse array of pharmaceutically active 5-substituted 1H-tetrazole derivatives through a multicomponent coupling reaction involving substituted aldehydes, malononitrile, and sodium azide as key components. A noteworthy feature of this approach is its adherence to environmentally friendly reaction conditions, thus making it superior in comparison to previously established methodologies. Furthermore, a plausible mechanistic pathway has been proposed to elucidate the impressive performance of the developed catalytic system in the targeted reaction. It is anticipated that the current research will not only contribute to the purposeful designing of advanced magnetic MOF-based architectures but will also play a pivotal role in promoting sustainable practices in industrial processes, addressing pressing environmental and economic concerns.

Mechanochemical Synthesis of α-halo Alkylboronic Esters.

α-halo alkylboronic esters, acting as ambiphilic synthons, play a pivotal role as versatile intermediates in fields like pharmaceutical science and organic chemistry. The sequential transformation of carbon-boron and carbon-halogen bonds into a broad range of carbon-X bonds allows for programmable bond formation, facilitating the incorporation of multiple substituents at a single position and streamlining the synthesis of complex molecules. Nevertheless, the synthetic potential of these compounds is constrained by limited reaction patterns. Additionally, the conventional methods often necessitate the use of bulk toxic solvents, exhibit sensitivity to air/moisture, rely on expensive metal catalysts, and involve extended reaction times. In this report, a ball milling technique is introduced that overcomes these limitations, enabling the external catalyst-free multicomponent coupling of aryl diazonium salts, alkenes, and simple metal halides. This approach offers a general and straightforward method for obtaining a diverse array of α-halo alkylboronic esters, thereby paving the way for the extensive utilization of these synthons in the synthesis of fine chemicals.

Modular assembly of arenes, ethylene and heteroarenes for the synthesis of 1,2-arylheteroaryl ethanes.

The 1,2-arylheteroaryl ethane motif stands as a privileged scaffold with promising implications in drug discovery. Conventional de novo syntheses of these molecules have relied heavily on pre-functionalized synthons, entailing harsh conditions and multi-step processes. Here, to address these limitations, we present a modular approach for the direct synthesis of 1,2-arylheteroaryl ethanes using feedstock chemicals, including ethylene, arenes and heteroarenes. We disclosed a photo triplet-energy-transfer-initiated radical cascade process, leveraging homolytic cleavage of C-S bonds in aryl sulfonium salts as the key step to access aryl radicals with excellent regioselectivity. This method allows for rapid structural diversification of bioactive molecules, showcasing excellent functional group tolerance and streamlining the synthesis of bioactive compounds and their derivatives. Furthermore, our approach can be extended to propylene, non-gaseous terminal alkenes and various other electrophilic radical precursors, including heteroaryl radicals, hydroxyl radicals, trifluoromethyl radicals and α-carbonyl alkyl radicals. This study highlights the significance of radical polarity matching in designing selective multi-component couplings.

Electrosynthesis of Tetrasubstituted Sulfonated Pyrazoles through Iodide‐Mediated Multicomponent Coupling

Electrosynthesis of Tetrasubstituted Sulfonated Pyrazoles through Iodide‐Mediated Multicomponent Coupling

Copper-Catalyzed Multicomponent Coupling Reaction of Primary Aromatic Amines, Rongalite, and Alkynes: Access to N-Aryl Propargylamines.

In this work, a practical copper-catalyzed multicomponent coupling reaction of primary aromatic amines, rongalite, and alkynes for the direct synthesis of N-aryl propargylamines has been developed. This method could overcome the substrate limitation in A3 coupling reactions of primary aromatic amines, formaldehyde, and alkynes. Mechanistic studies revealed that rongalite acts as not only the active C1 unit but also the accelerator to activate the in situ-generated N-arylmethanimines for the coupling reaction with alkynes. This coupling reaction is highly efficient and features a broad substrate scope, as well as utility with scale-up synthesis and converting the corresponding product N-aryl propargylamines into useful heterocyclic skeletons.

Organoselenium-Catalyzed C2,3-Diarylation of N-H Indoles.

An organoselenium-catalyzed C2,3-diarylation of unprotected N-H indoles with electron-rich aromatics has been developed. This one-pot multicomponent tandem cross-dehydrogenation coupling reaction allows for the incorporation of two different aromatic groups to indoles. More importantly, this approach offers significant advantages, including a high atom and step economy, eliminating the need for prepreparation of the reaction substrates, streamlining the synthetic process and enhancing its practicality. Overall, this organoselenium-catalyzed C2,3-diarylation reaction presents an efficient and versatile strategy for the functionalization of indole derivatives.

Coupling Mechanism of Multiple-Thermal-Fluid Multi-Cycle Stimulation in Ultra-Heavy-Oil Reservoirs

Multiple-thermal-fluid (MTF) stimulation technology has been successfully applied in heavy-oil reservoir development, resulting in the significant enhancement of oil production. However, the underlying mechanism of multi-component coupling remains unclear. This paper constructs a coupling model for MTF stimulation, investigates the coupling mechanism of different media in various zones during multiple-cycle stimulation operations, and compares the implementation effect with field results. The findings reveal that (1) based on media distribution, the area from near-wellbore to far well locations can be divided into four zones: high-temperature oil-viscosity-reduction zones, compound action zones, energy-replenishment zones, and unaffected zones. (2) In the high-temperature oil-viscosity-reduction zone, the latent heat of vaporization is released by steam, and ultra-heavy oil absorbs heat and reduces its viscosity, which plays a dominant role in the production of MTF. In the compound action zone, hot water, CO2, and N2 exhibit a synergistic effect which enhances overall performance. In the energy-replenishment zone, a small amount of N2 provides pressure maintenance and an additional energy supply. (3) As more cycles of stimulation are conducted, the compound action zone expands, while the energy-replenishment zone contracts. Simultaneously, there is a decrease in contribution rate from the high-temperature viscosity-reduction zone to oil production but an increase from both the compound action zone and energy-replenishment zone up to 30%. Based on the dynamic law of representative wells, this paper proposes a multi-media zonal coupling mechanism, providing a reference for subsequent research on MTF stimulation mechanisms and the adjustment of production measures.

Nickel-catalyzed multicomponent 1,4-fluoroalkylcarbonylation of 1,3-enynes to access allenyl ketones

Allenyl ketones are widely distributed in various bioactive molecules which lead their selective synthesis continues a hot research topic. Currently, most of the developed protocols require multistep and stoichiometric reactions together with noble metal catalysts. Herein, we developed a practical methodology to access allenyl ketones straightforwardly via multi-component coupling of 1,3-enynes, fluoroalkyl halides, arylboronic acids, and CO with nickel as the catalyst. A series of fluoroalkyl unit containing allenyl ketones were produced in moderate to good yields. This new procedure features cheap catalytic system, relatively mild reaction conditions, broad substrate scope, excellent regioselectivity, and attractive synthetic transformations of the obtained products.

Reduced Graphene Oxide Modified Nitrogen-Doped Chitosan Carbon Fiber with Excellent Electromagnetic Wave Absorbing Performance.

Lightweight and low-cost one-dimensional carbon materials, especially biomass carbon fibers with multiple porous structures, have received wide attention in the field of electromagnetic wave absorption. In this paper, graphene-coated N-doped porous carbon nanofibers (PCNF) with excellent wave absorption properties were successfully synthesized via electrostatic spinning, electrostatic self-assembly, and high-temperature carbonization. The obtained results showed that the minimum reflection loss of the absorbing carbon fiber obtained under the carbonization condition of 800 °C is -51.047 dB, and the absorption bandwidth of reflection loss below -20 dB is 10.16 GHz. This work shows that carbonization temperature and filler content have a certain effect on the wave-absorbing properties of fiber, graphene with nanofiber, and the design and preparation of high-performance absorbing materials by combining the characteristics of graphene and nanofibers and multi-component coupling to provide new ideas for the research of absorbing materials.

Multicomponent Reductive Coupling for Selective Access to Functional γ-Lactams by a Single-Atom Cobalt Catalyst.

Despite their significant importance to numerous fields, the difficulties in direct and diverse synthesis of α-hydroxy-γ-lactams pose substantial obstacles to their practical applications. Here, we designed a nitrogen and TiO2 co-doped graphitic carbon-supported material with atomically dispersed cobalt sites (CoSA-N/NC-TiO2), which was successfully applied as a multifunctional catalyst to establish a general method for direct construction of α-hydroxy-γ-lactams from cheap and abundant nitro(hetero)arenes, aldehydes, and H2O with alkynoates. The striking features of operational simplicity, broad substrate and functionality compatibility (>100 examples), high step and atom efficiency, good selectivity, and exceptional catalyst reusability highlight the practicality of this new catalytic transformation. Mechanistic studies reveal that the active CoN4 species and the dopants exhibit a synergistic effect on the formation of key acid-masked nitrones; their subsequent nucleophilic addition to the alkynoates followed by successive reduction, alkenyl hydration, and intramolecular ester ammonolysis delivers the desired products. In this work, the concept of reduction interruption leading to new reaction route will open a door to further develop useful transformations by rational catalyst design.

Copper-Assisted (Pseudo-)Halochalcogenation of Arynes.

In this report, we describe the multicomponent coupling reaction between arynes, (pseudo)halides, and an electrophilic chalcogen species. Addition of a copper salt enabled smooth conversion by suppressing side reactions. A variety of different aryne precursors as well as seleno- and thiosulfonates were employed, yielding a broad spectrum of ortho-(pseudo)halogenated chalcogenides. This motif was subjected to different cross-coupling approaches, demonstrating the applicability of these compounds as building blocks for more complex structures.

Olefin Difunctionalization for the Synthesis of Tetrahydroisoquinoline, Morpholine, Piperazine, and Azepane.

This report outlines a versatile strategy for synthesizing a diverse array of N-heterocycles. By the utilization of common olefins, this simple protocol facilitates their coupling with various bifunctional reagents. Furthermore, it can be integrated with C-H amination techniques to directly produce N-heterocycles in a multicomponent cascade coupling process. The unique bond disconnection logic employed in this process underscores its efficiency in achieving rapid simplification through cascade couplings.

Study on the synergistic effect of calcium carbide residue -fly ash enhanced desulphurisation gypsum under high temperature maintenance condition

The preparation of cementitious materials from bulk industrial solid waste is an effective way to replace cement. Based on the multi-component synergistic coupling effect, the influence law of different dosage of fly ash (FA) and calcium carbide residue (CCR) on the performance of flue-gas desulfurization gypsum (FGDG) slurry was investigated, and the hydration process of composite cementitious materials was discussed through the analysis of hydration products, micro morphology and pore structure by the characterisation methods such as XRD, FTIR, MIP and SEM-EDS. The results show that FA incorporation can improve the flow properties of the slurry, and under the action of CCR and FGDG, the alkalinity of the whole system rises, and the FA vitreous body undergoes dissolution corrosion, releasing reactive SiO2 and Al2O3, and forming C-S-H gel and AFt. In addition, some of the tiny FA particles fill up the pore spaces and microcracks, and the structure becomes denser, and all these effects together contribute to the development of the mechanical properties. This research is conducive to the application of new green cementitious materials and promotes the resourceful use of industrial solid waste.

Organophotocatalytic access to C-glycosides: multicomponent coupling reactions using glycosyl bromides.

Photochemical multi-component coupling reactions initiated by the activation of glycosyl bromides in the presence of 1,4-bis(diphenylamino)benzene (BDB) as an organic photocatalyst were developed. C-glycosides accompanied by olefin (di)functionalization were obtained. This method allows us to access various C-glycosides with alkene, carbonyl, alcohol, ether, and amide functionalities.

Modular synthesis of α-branched secondary alkylamines via visible-light-mediated carbonyl alkylative amination.

The development of methods for the assembly of secondary α-alkyl amines remains a central challenge to chemical synthesis because of their critical importance in modulating the physical properties of biologically active molecules. Despite decades of intensive research, chemists still rely on selective N-alkylation and carbonyl reductive amination to make most amine products. Here we report the further evolution of a carbonyl alkylative amination process that, for the first time, brings together primary amines, aldehydes and alkyl iodides in a visible-light-mediated multicomponent coupling reaction for the synthesis of a wide range of α-branched secondary alkylamines. In addition to exploring the tolerance and limitations in each reaction component, we also report preliminary applications to the telescoped synthesis of α-branched N-heterocycles and an N-alkylation protocol that is selective for primary over cyclic secondary amines. Our data support a mechanism involving addition of an alkyl radical to an uncharged alkyl imine which, to the best of our knowledge, has not previously been described. We believe that this method will enable practitioners of synthetic chemistry in academic and industrial settings to approach the synthesis of these important molecules in a manner that is streamlined compared to established approaches.