Addition Of Anions Research Articles

Detection of Silver and Mercury Ions Using Naphthalimide-Based Fluorescent Probe.

A multifunctional fluorescent probe P based on a naphthalimide derivative for the detection of Ag+ and Hg2+ through a dual-signal was designed and characterized. P exhibited a large Stokes shift (107 nm), high selectivity, good sensitivity, and fast response time. By adjusting the testing medium and the order of reagent addition, multifunctional detection with P was achieved. The addition of Ag+ or Hg2+ to P solution in either ethanol or an ethanol-water mixture resulted in a significant quenching of fluorescence emission at 537 nm and caused a decrease in the absorbance at 440 nm accompanied by the appearance of a new absorption peak at around 340 nm, and there was an obvious color change from yellow to colorless. In contrast, the addition of other common metal ions and anions did not produce substantial spectral or color changes. The detection limit of probe P for Ag+ and Hg2+ was calculated to be 0.33 μM. The sensing mechanism was proposed and validated through MS and 1H NMR spectrometry methods. Additionally, P demonstrated the capability to recognize Ag+ and Hg2+ in living cells with satisfactory results.

The role of iron(II) excess and phosphate to synthesize hydroxychloride green rust

Green rust (GR) is a chemically reactive mineral of interest for environmental remediation. However, the lack of stability of this compound is a major drawback for practical applications. In this study, the precipitation of hydroxychloride green rust type 1 (GR1Cl) from soluble FeII and FeIII species was studied by analyzing pH titration curves and employing XRD, Raman and Mössbauer spectroscopies to find optimal conditions for synthesizing GR1Cl. Using the stoichiometric condition for FeII-FeIII corresponding to the [FeII3FeIII(OH)8]Cl compound, FeIIIO(OH)2.9Cl0.1 was formed in a first step during the addition of NaOH and then transformed into a mixture of GR1Cl and Fe3O4. The addition of phosphate anions (PO4) at a molar ratio PO4: Fe = 1: 10 in the initial solution was shown to avoid the formation of undesired magnetite. Interestingly, GR1Cl was also the only product without adding PO4 using an excess of FeII species in solution, i.e. for an initial ferric molar fraction x = FeIII: Fetot of 0.2. First experimental evidences of a hydroxyphosphate green rust type 2 GR2PO4 were also provided by XRD and Raman spectroscopy. Therefore, this work may attract interest for a better understanding of the geochemical cycle of iron and phosphate in natural environments such as hydromorphic soils or hydrothermal chimneys where fougerite, the mineral homologue of synthetic GR, is supposed to play a significant role.

Synthesis, crystal structure and sulphide ion sensing study of a Cu(II) complex of aroyl hydrazone

Herein, we report a Cu(II) complex {[CuII(HL)(H2O)2]Cl} of a benzoylhydrazone Schiff base ligand (4-((2-benzoylhydrazineylidene)methyl)-3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-1-ium chloride) (H2L). The molar conductance in solution, magnetic susceptibility, ESI-MS and EPR spectroscopy have been performed to justify the structure of the complex. The solid-state structure of the complex has also been solved by single crystal X-ray diffractometry. Cu(II) centre is penta-coordinated with imine-N, phenoxide-O and deprotonated amide-O donor of the ligand and two H2O molecules occupying the coordination sphere forming a distorted square pyramidal geometry (τ = 0.32). We have studied the anion sensing property of the complex by monitoring the changes in the UV–Vis and fluorescence spectra of the complex in aqueous Tris-HCl buffer medium with incremental addition of various anions of tetrabutylammonium salt. The complex shows appreciable sensitivity toward sulphide ion, among various other anions, with association constant (Kb) for binding of the complex with S2− and lowest detection limit (L.O.D) value of 6.87 × 104 M−1 and 6.9 × 10−7 M, respectively. Thus, the complex can be used as an efficient S2− probe. The mechanism of sensing is found to be displacement of the fluorescent ligand from the Cu(II) complex by the sulphide ion.

Photocatalytic ZnIn2S4 for 2-Mercaptobenzothiazole Degradation: Facile Synthesis, Influencing Factors and Mechanism

The development of an efficient, stable and environmentally friendly semiconductor photocatalyst is great research significance in the field of environment and energy. In this paper, ZnIn2S4 semiconductor photocatalysts with flower-like hierarchies were prepared by simple and environmentally friendly method. The influence of ZnIn2S4 dosage, pH and different inorganic salt ions on the photocatalytic degradation of 2-mercaptobenzothiazole (MBT) under visible light was investigated in detail. The results showed that the photocatalyst dosage was 0.05 g, and the photocatalytic degradation efficiency of MBT was the highest in the weakly acidic environment with pH was five. Meanwhile, the addition of some inorganic anions has a significant inhibitory effect on the photocatalytic activity of ZnIn2S4 semiconductor photocatalyst, while cations have less effect. Moreover, the ZnIn2S4 semiconductor photocatalyst had excellent stability and recyclability, and its photodegradation mechanism had been deeply studied. This work provides a theoretical and experimental foundation for exploring the different influencing factors of photocatalytic degradation of organic pollutants in wastewater by other semiconductors.

Retrosynthetic Pathways of Decahydrofluorene-Alkaloid Microascones B

Microascones B is a compound that can be a candidate for antibacterial material and is discovered and obtained from marine-derived fungus with complex 12- or 13- membered ring structures. Since no one has provided the forward synthesis and retrosynthesis pathway, we have introduced a possible retro-synthesis pathway in this work. The retrosynthesis of this complicated compound can be done in several steps into starting materials. Some of the core retrosynthesis strategies contain the analysis of di-oxygenation patterns to break bonds retro-synthetically by applying aldol reactions and Grignard as well as anion addition. Moreover, the Diels-Alder reaction is also one of the core reactions to break those multiple rings in this retrosynthesis pathway

Dearomative Addition of Carboranyl Anions to Isoquinolinium Salts and Subsequent Reduction to Access Carborane‐Functionalized 1,2‐Dihydroisoquinolines and 1,2,3,4‐Tetrahydroisoquinolines

AbstractA dearomative addition of readily available carboranyllithium reagents to isoquinolinium salts gave a series of carborane cage C‐substituted 1,2‐dihydroisoquinolines in 43–85 % yields. Subsequent hydrogenation enabled the facile synthesis of corresponding carboranyl 1,2,3,4‐tetrahydroisoquinolines in 65–95 % yields. The addition‐reduction pathway is applicable to a wide range of substituted isoquinolinium salts and o‐carborane or m‐carborane.

Si-Linked Glycomimetics through a Stereoselective Silicon Transfer and Anion Addition.

We report a synthesis of silicon-linked glycomimetics, demonstrating unique structural properties and metabolic stability due to the inertness of the C-Si bond. Our method focuses on the stereoselective transfer of silicon and anion addition, revealing that chirality at the silicon atom can be controlled through kinetic resolution. This approach allows for the selective generation of 1,2-cis and 1,2-trans isomers via the manipulation of C2-protected silicon ethers and nucleophilic opening of glycal epoxides. We achieved high selectivity at the anomeric carbon and expanded the scope to include various saccharides and substituted silanes. Our findings indicate that silicon transfer occurs intramolecularly and is influenced by the nature of the counterion and reaction conditions. Additionally, chiral silanes produced through our method hold promise for medicinal chemistry applications, addressing significant gaps in the synthesis and utility of glycomimetics. This work opens new avenues for the development of bioactive silicon-based molecules.

Bifunctional catalytic activity of anion-doped LaSrCoO4 for oxygen reduction and evolution reactions.

Here, we synthesized Co-based, anion-incorporated‍ ‌R‌u‌d‌d‌l‌e‌s-d‌e‌n‌-‌Popper perovskite electrocatalysts (LaSrCoO4-x X y ) and compared their catalytic performances in the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The ORR mechanism with the newly synthesized F-doped LaSrCoO4 catalyst was dominated by a four-electron process, and the number of electrons involved in the reaction increased compared with that for LaSrCoO4. The OER activity of the hydride-doped LaSrCoO4 catalyst was the highest among the LaSrCoO4 system catalysts. Density functional theory calculations revealed that there is a correlation between the Co 3d unoccupied orbital band centre and the OER activity. The addition of anions and substitution of metal sites improved the ORR and OER activities of the catalysts. Our findings confirmed that the addition of heteroatom anions can improve the activity of perovskite-type electrocatalysts, promoting their application in various fields.

Yield stress and zeta potential-pH behaviour of washed spherical α-Al2O3 particles with anionic additives: Particle force and ChemBio 3D simulation

The yield stress- and zeta potential-pH behaviour of washed spherical α-Al2O3 suspension with and without three typical anionic additives were characterized. The zero zeta potential or isoelectric point (IEP) of washed α-Al2O3 particles locates at pH∼ 9.5. With the increased dosage of the anionic additives, IEP moves to a lower pH range. The maximum yield stress of 50 wt% α-Al2O3 suspension decreases from 78.3 Pa to 50 Pa by about 36 % when citric acid is 0.2 dwb% (dispersant g/100 g powder). According to the simulation of the MM2 model, the type of O-H···O hydrogen bond existed in the CA molecule which results in a stable steric repulsive effect. The pH range where yield stress exists also moves to the lower pH with the addition of anionic additives. However, the addition of Diisobutylene-maleic anhydride sodium salt and Polystyrene sulphonic acid sodium salt increase the maximum yield stress because of the specific attraction force, hydrophobic attraction force and charge attraction force.

DEGRADATION KINETICS OF TEXTILE AZO DYE REACTIVE ORANGE-16 BY GAMMA IRRADIATION

Gamma radiation have become attention since their high potential for degrading compounds, especially organic pollutants. In this research, gamma radiation was studied for degrading the Reactive Orange-16 (RO-16) dye, a toxic and carcinogenic pollutant. The radiolytic degradation process was studied in a batch reactor with a gamma-ray dose rate of 2.930 kGy/h. The effect of experimental variable such as initial peroxide concentration, initial pH, initial dye concentration, and addition of inorganic anion were studied. The highest degradation rates were achieved at a peroxide concentration ranging from 2 to 4 mM. In contrast, the higher peroxide concentration indicated the slower degradation process caused by the scavenging effect of the peroxide. Degradation of 88% RO-16 dye with 0.1 mM initial concentration, was achieved at 2.0 kGy irradiation dose and 97.4% degradation in the presence of 4 mM peroxide. The dose constant (d) for those degradation processes was 1.0657 kGy-1 and 1.8420 kGy-1 respectively. The degradation was more efficient in acid pH. The degradation process increased with lower initial dye concentrations. The degradation of RO-16 dye by gamma-ray was inhibited by the presence of inorganic anions in the following sequence: NO3-→ CO32− → HCO3− → CH3COO-→ Cl-.

K3PO4–Mediated Synthesis of Chromeno–[3,4‐c]isoxazole from 3–Nitro–2H–chromene and α–Chloro Aldehyde via Michael Addition/C−Cl Bond Cleavage/Deformylation as Key Fragmentation Sequences

AbstractHere we report a transition metal– and oxidant–free annulation cascade method for the synthesis of chromeno–isoxazoles. The annulation reaction involves easily accessible starting materials, 3‐nitro‐2H‐chromene and α‐chloro aldehyde, yielding the structurally intriguing framework, chromeno[3,4‐c]isoxazoles employed by tripotassium phosphate as a base. The isoxazole ring construction over the 2H–chromene unit is believed to occur via a series of multiple reaction sequences. Here, the enolate generation/Michael addition/C−Cl bond cleavage/oxy–anionic addition to reactive tethered‐aldehyde/deformylation via retro–C−C and N−O bond cleavages are the most possible sequences which furnish the desired end–product in good chemical yields. The multiple reaction sequences occur in one‐pot at mild conditions, supported by experimental results and a few control experiments including DFT studies. This process exhibits a broad substrates scope illustrating good functional group compatibility towards both the nitrochromenes and aldehydes, and thus prove to be a general and efficient protocol for the synthesis of chromeno[3,4–c]isoxazoles. Overall, the use of nitrochromene as the limiting reagent, noteworthy functional group tolerance, scalability including great applications like chiral pool strategy towards the synthesis of enantioenriched chromeno‐isoxazole are the additional features.

Anion-binding-induced selective aggregation and self-degradation: Influence of positional isomerism on the anion selectivity and mode of binding of an imine-based receptor

Imine based positional isomers (8E)-N-(4-((E)-(perfluorophenylimino)methyl)benzylidene)-2,3,4,5,6-pentafluorobenzenamine, L and (10E)-N-(3-(E-Perfluorophenylimino)methyl)benzylidene)-2,3,4,5,6-pentafluorobenzenamine, L1 have been designed, and synthesized by functionalizing two electron deficient aromatic moieties at the para–para’/ortho-ortho’ positions in the phenyl core of the L and L1 respectively. The responses of L and L1 towards various anionic species are examined. The positional isomers L and L1 differs not only by showing distinguishable color change upon addition of anions but also differentiates themselves by the way of self-assembling together upon binding with cyanide anion. The naked-eye colorimetric experiments, UV–Vis, Nuclear Magnetic Resonance, and Infra-Red spectroscopic analyses reveal that the isomer L binds fluoride anion through 2:1 stoichiometry ratio. Unlike fluoride complex, the isomer L form aggregates while binding with cyanide ion. On the other hand, isomer L1 does not show any instant color change upon additions of any anion. Interestingly, after thirty minutes, only the color of the cyanide complex is turned into dark brown. While analyzing the spectroscopic results of cyanide complex of L1, it is found that the cyanide complex begins to decompose and finally it is completely decomposed within 30 min. This unprecedented phenomenon about the colorimetric sensing of cyanide and destruction of cyanide complex with respect to time has not been reported in the literature yet. To the best of our knowledge this is the first example of study of sensing controlling the selectivity, mode of binding, self-aggregating and degradation properties of anionic complexes under the influence of positional isomeric effects. This present investigation provides simple and effective strategy to construct the sensor molecules with tunable binding properties in terms of easy to prepare as well as easy to use as a colorimetric sensor._____________________________________________________________________________________________________

Electro-Oxidation of Cumene Using Diamond Electrodes in Batch and Flow

Selective oxidation of aromatic alkyl side chains is an important molecular transformation process to obtain various materials ranging from rubber and resin to fine chemicals. Generally, molecular oxygen has been utilized in straightforward oxidation of aromatic alkyls. However, since molecular oxygen is highly stable, activation of the molecular oxygen itself is necessary, which requires a specific catalyst and/or harsh condition such as high temperature and high pressure. Recent environmental and sustainable concerns lead to a growing demand for the development of greener oxidation processes.Recently, electro-organic synthesis, referring to an organic synthesis method combined with electrochemistry, has drawn attention as a sustainable synthetic method. Since electro-organic synthesis utilizes electricity itself as a reagent, reactions proceed well even under ambient conditions and reagent wastes are reduced to a minimum. In electro-organic synthesis, electrode materials are one of the most significant parameters because reactions occur at the anode and/or cathode. Boron-doped diamond (BDD) is a relatively new electrode material and shows a wide potential window, which can be applied to the transformation of compounds with high redox potentials. Therefore, BDD electrodes would enable a straightforward oxidation reaction of aromatic alkyls, which is difficult to achieve with other conventional electrode materials.Herein, we report the straightforward electro-oxidation of cumene, one of the most important and extensively investigated aromatic alkyls, by BDD electrodes. The role of electrode materials was investigated with electrochemical measurements. Furthermore, the cell design (i.e. batch vs. flow) was examined, and we realized that the product selectivity of cumene oxidation can be switched by simply changing the cell design.First, we carried out the electrolysis of cumene under the constant current condition in an undivided batch cell. The main product was acetophenone under the following optimum conditions: (solvent) MeCN, (supporting electrolyte) Et4NClO4, (current density) 2.1 mA/cm2, (amount of charge) 5 F referring to mole of cumene. It should be noted that almost no acetophenone was obtained when the combination of anode and cathode was graphite/graphite or Ni/Ni. Cyclic voltammetry using BDD as a working electrode showed a clear oxidation peak of cumene at around 2.40 V (vs. Ag/Ag+). On the other hand, no clear oxidation peak was observed when using graphite or Ni as a working electrode. This is because potential windows of graphite and Ni are too narrow to oxidize cumene directly. Overall, the electrochemical measurements indicate the BDD’s wide potential window enables direct oxidation of cumene to produce a key reaction intermediate to afford acetophenone. A series of electrolysis experiments confirmed that the reaction intermediate is the cumyl cation and the oxygen source is the superoxide generated by reduction of dissolved oxygen on the cathode. A proposed mechanism is as follows. Anodic oxidation of cumene on the BDD electrode affords a cumyl cation. On the other hand, cathodic reduction of dissolved oxygen produces the superoxide and even the hydroperoxide anion. Addition of the hydroperoxide anion to the cumyl cation yields cumene hydroperoxide, which is further converted into acetophenone.Second, we carried out the electrolysis of cumene under the constant current condition in an undivided flow cell. The main product was a-cumyl alcohol under the following optimum conditions: (solvent) MeCN, (supporting electrolyte) Et4NClO4, (current density) 0.25 mA/cm2, (amount of charge) 1 F referring to mole of cumene, (flow rate) 0.375 mL/min. A series of flow electrolysis experiments indicated that cumene is converted into a-cumyl alcohol via cumene hydroperoxide, and then to acetophenone, which is supported by cyclic voltammetry measurements: the potential at which the current value increases was lower in the order of cumene hydroperoxide > a-cumyl alcohol > cumene > acetophenone. A proposed mechanism is as follows. A hydroperoxide anion generated at the cathode added to a cumyl cation generated at the anode to form cumene hydroperoxide. The O-O bond in cumene hydroperoxidewas cleaved anodically to form alkoxy radical, which underwent a hydrogen atom transfer (HAT) between cumene to yield a-cumyl alcohol and cumyl radical. Furthermore, a-cumyl alcoholwas oxidized into the alkoxy radical, followed by b-scission to yield acetophenone. Therefore, it is suggested that the selective conversion of cumene into a-cumyl alcohol in flow electrolysis was due to suppressing overoxidation of a-cumyl alcoholinto acetophenone. Figure 1

Visible-Light-Promoted Cascade Carboxylation/Arylation of Unactivated Alkenes with CO2 for the Synthesis of Carboxylated Indole-Fused Heterocycles.

Described here is a visible-light-promoted cascade carboxylation/arylation of indole-tethered unactivated alkenes with CO2 to access various carboxylated indole-fused heterocycles. This reaction is initiated by the addition of a CO2 radical anion to the alkene motif toward an alkyl carbon radical, followed by its addition to the aromatic ring, and then rearomatization to afford the final products. This reaction provides a facile and sustainable protocol for the construction of carboxylated indole-fused heterocycles using CO2 as the carboxylic source.

Role of anionic surfactant addition in improving thermoelectric properties of PEDOT:PSS free-standing films

Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) has recently gained interest as a potential candidate for small-scale thermoelectric conversion because of the facile doping, solution processability, and flexibility. However, the practical applications of PEDOT:PSS are limited by its comparatively low figure of merit (ZT) compared with inorganic thermoelectric materials. Herein, to further improve the thermoelectric properties of PEDOT:PSS, we investigated the role of the addition of surfactants, sodium dodecyl sulfate, sodium dodecyl benzenesulfonate (SDBS) or Triton X-100, to the PEDOT:PSS free-standing films on their thermoelectric properties. We showed that the addition of the surfactant improved the film crystallinity, significantly improving the electrical conductivity. The highest conductivity was obtained for anionic surfactant SDBS at a 0.94 wt% concentration. Moreover, the inclusion of the surfactant reduced the thermal conductivity while maintaining a relatively constant Seebeck coefficient, consequently improving the ZT value. Furthermore, a flexible thermoelectric device crafted from the as-fabricated PEDOT:PSS/SDBS sheets was developed to explore the potential applications of wearable electronics using low-grade thermal energy. Overall, we indicate the significance of surfactants in enhancing the thermoelectric properties of free-standing PEDOT:PSS films in this study.

A novel dual channel six-membered spirorhodamine for Cu2+ and ClO- depending on solvent and application in real samples and bioimaging

To reveal the solvent dependence of six-membered rhodamine spirocycles (SMRS), a new probe SM-RB has been synthesized and investigated the spectral properties in different solvents upon the addition of various metal ions and anions. SM-RB exhibited high selectivity for Cu2+ in CH3CN/HEPES and ClO- in C2H5OH/HEPES solutions, respectively. The spectral changes of SM-RB in the presence of ClO- in C2H5OH/HEPES solution were much less than that of Cu2+ in CH3CN/HEPES. The detection limit of Cu2+ was as low as 36 nM (fl) in CH3CN/HEPES. The kinetic equilibration time (8 s) indicated that the two solvent systems did not delay the spectral response speed to Cu2+ and ClO-. Solvent systems influenced the pKa value of SM-RB in CH3CN/HEPES and C2H5OH/HEPES. The pKa value of SM-RB was 4.34 (±0.7) (Abs) and 4.75 (±0.14) (Fl) in CH3CN/H2O, but can’t be exactly calculated by pH titration in C2H5OH/H2O. The reversibility and Job plot of SM-RB were investigated to propose the response mechanism of SM-RB with Cu2+ and ClO- in the two solvent systems. Finally, SM-RB not only can be used for the quantitative detection of copper ions in grape peel, but also can real-time monitor the fluctuation of Cu2+ in lysosomal pools.

Insight into Fluoride Additives to Enhance Ammonia Production from Lithium-Mediated Electrochemical Nitrogen Reduction Reaction.

Demands for green ammonia production increase due to its application as a proton carrier, and recent achievements in electrochemical Li-mediated nitrogen reduction reactions (Li-NRRs) show promising reliability. Here, it is demonstrated that F-containing additives in the electrolyte improve ammonia production by modulating the solid electrolyte interphase (SEI). It is suggested that the anionic additives with low lowest unoccupied molecular orbital levels enhance efficiency by contributing to the formation of a conductive SEI incorporated with LiF. Specifically, as little as 0.3wt.% of BF4 - additive to the electrolyte, the Faradaic efficiency (FE) for ammonia production is enhanced by over 15% compared to an additive-free electrolyte, achieving a high yield of 161 ± 3nmol s-1 cm-2. The BF4 - additive exhibits advantages, with decreased overpotential and improved FE, compared to its use as the bulk electrolyte. The observation of the Li3N upper layer implies that active Li-NRR catalytic cycles are occurring on the outermost SEI, and density functional theory simulations propose that an SEI incorporated with LiF facilitates energy profiles for the protonation by adjusting the binding energies of the intermediates compared to bare copper. This study unlocks the potential of additives and offers insights into the SEIs for efficient Li-NRRs.

Chemoselective Synthesis of Cyanoformamides from Isocyanates and a Highly Reactive Nitrile Anion Reservoir

The direct addition of a nitrile anion to isocyanates is reported for a straightforward preparation of valuable cyanoformamides. Through the proper activation of an adequate silicon‐ate complex precursor (PhMe2SiCN) with a Lewis base (potassium tert‐amylate) under Barbier‐type conditions, the cyanide was instantaneously released, thus yielding the desired motif with full chemocontrol. No particular structural restriction was noticed for engaging in the transformation a wide series of commercially available isocyanates.

Tailoring Plasmonic Fields with Shape-Controlled Single-Crystal Gold Metasurfaces.

Geometry and crystallinity play a critical role in the wavelength-dependent optical responses and plasmonic local near-field distributions of metallic nanostructures. Nevertheless, the ability to tailor the shape and position of crystalline metal surface nanostructures has remained a challenge that limits control of their enhanced local fields and represents a barrier to harnessing their individual and collective responses. Here, we describe a solution deposition method in the presence of anionic additives, which yields shape-controlled, single-crystal plasmonic gold nanostructures on Ag(100) and Au(100) substrates. Use of SO42- ions yields smooth Au(111)-faceted square pyramids with large plasmonic Raman enhancements. Halide additives produce textured hillocks comprising edge- and screw-type dislocations (Cl-), or platelets with large-area Au(100) terraces and (110) step edges (Br-), while SO42- and Br- additive combinations provide Au(110)-faceted square pyramids. With lithographic patterning, this chemistry yields metal deposition with precise geometry and location control to provide single-crystal, plasmonic gold metasurfaces with tailored optical response. The appropriately designed metasurfaces can then generate large Raman scattering enhancements, far greater than high density gold square pyramids with random surface disposition. Shape-controlled single-crystal plasmonic metasurfaces will thus offer opportunities to tune the characteristics of nanostructures, providing enhanced optical, photocatalytic, and sensory response.

Tetraaryl-3H-Azepines: KOBut/DMSO-Catalyzed Assembly from Diaryldiynes and N-Benzylaldimines.

Di(het)aryldiynes smoothly react with N-benzylaldimines in a [4 + 3] cycloaddition manner under the action of the KOBut/DMSO system (60 °C, 30 min) to afford pharmaceutically relevant tetra(het)arylsubstituted 3H-azepines in up to 71% yield. The process involves the addition of azaallyl anions to one of the triple bonds of diynes followed by prototropic isomerization and cyclization of anionic intermediates with participation of the second triple bond. The cascade mechanism is consistent with quantum-chemical analysis (B2PLYP-D3/6-311+G**//B3LYP-D3/6-31+G* + PCM).