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Because of eco-friendliness, biodegradability and ease of modification, cellulose is deemed as alternative to unrenewable petroleum resources. Nonetheless, it is more indispensable to exploit corn cob cellulose produced from agricultural waste residue as supportive materials in green catalysis. In this study, a new magnetically benzimidazole functionalized cellulose/Fe3O4 derived from corn cob cellulose as a stabilizer agent (Fe3O4@CL-NHC) was prepared, and palladium was immobilized on this stabilizer (Fe3O4@CL-NHC-Pd). The catalyst was fully characterized by different techniques including TEM, SEM, and XPS analyses, etc. The abundant hydroxyl groups of cellulose provided uniform dispersion and high stability of palladium, while Fe3O4 as a support offered simple magnetic separation. High efficiency (up to 99 %) was demonstrated by this biocatalyst under green conditions in relatively short reaction times towards Suzuki reactions. Due to collaborative interactions of N-heterocyclic carbene and hydroxyl groups with palladium, the synthesized complex prevented metal leaching effectively (<1 %). Moreover, the magnetic property of this catalyst (43.0 emu g-1) provides facile recovery of this composite from the reaction mixture with great ease for several times, which overcomes issues of complicated work-up separation. This work offers a promising avenue to enriching the application of biopolymer from agricultural residue in the potential organic transformations.

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We have developed an innovative mesoporous nanocatalyst by carefully attaching a 2-aminothiophenol-Cu complex onto functionalized MCM-41. This straightforward synthesis process has yielded a versatile nanocatalyst known for its outstanding efficiency, recyclability, and enhanced stability. The structural integrity of the nanocatalyst was comprehensively analyzed using an array of techniques, including BET (Brunauer-Emmett-Teller) for surface area measurement, ICP (Inductively Coupled Plasma) for metal content determination, EDS (Energy-Dispersive X-ray Spectroscopy) for elemental mapping, XRD (X-ray Diffraction) for crystalline structure elucidation, SEM (Scanning Electron Microscopy), EMA (Elemental Mapping Analysis), TEM (Transmission Electron Microscopy), TGA (Thermogravimetric Analysis), FT-IR (Fourier Transform Infrared Spectroscopy), AFM (Atomic Force Microscopy), and CV (cyclic voltammetry). Subsequently, the catalytic properties of the newly developed MCM-41-CPTEO-2-aminothiophenol-Cu catalyst was evaluated in the synthesis of biphenyls, demonstrating outstanding yields through a Suzuki coupling reaction between phenylboronic acid and aryl halides. Importantly, this reaction was conducted in an environmentally friendly medium. Note the remarkable recyclability of the catalyst, proving its sustainability over six cycles with minimal loss in activity additionally hot filtration test was prepared to examine the stability of this nanocatalyst. This outstanding feature emphasizes the catalyst's potential for long-term, environmentally conscious catalytic applications.

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Palladium serves as a multi-functional catalyst which is controllable by tuning reaction conditions. This work demonstrated the utilization of a palladium catalyst for the synthesis of phenanthrenols by cascade palladium-catalyzed Suzuki/Heck reaction between chalcone and 2-bromophenylboronic acid, followed by Michael addition. The sequential reaction could be controlled by reactivity of the palladium catalyst in different solvents and concentrations of reagents. This protocol could be applied to a broad range of substrates to give products in low to good yields.

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A series of 10 cyclic, biaryl analogs of enkephalin, with Tyr or Phe residues at positions 1 and 4, were synthesized according to the Miyaura borylation and Suzuki coupling methodology. Biaryl bridges formed by side chains of the two aromatic amino acid residues are of the meta-meta, meta-para, para-meta, and para-para configuration. Conformational properties of the peptides were studied by CD and NMR. CD studies allowed only to compare conformations of individual peptides while NMR investigations followed by XPLOR calculations provided detailed information on their conformation. Reliability of the XPLOR calculations was confirmed by quantum chemical ones performed for one of the analogs. No intramolecular hydrogen bonds were found in all the peptides. They are folded and adopt the type IV ß-turn conformation. Due to a large steric strain, the aromatic carbon atoms forming the biaryl bond are distinctly pyramidalized. Seven of the peptides were tested in vitro for their affinity for the µ-opioid receptor.

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A series of novel tricyclic quinazolinone-iminosugars 5 and their derivatives 7 were obtained from the tosylated sugars by three steps. Firstly, the reaction of the isopropylidene protected sugar tosylate 1 and o-aminobenzylamine 2 generated the precursor tricyclic quinazolin-iminosuar 3, which was then oxidized by KMnO4 to produce the corresponding quinazolinone 4. Finally, removal of the isopropylidene group yielded the target tricyclic quinazolinone iminosugars 5. In addition, quinazolinone-iminosugars 4ac, 4bc and 4cc who contain bromine in the aromatic region underwent Suzuki reaction with phenylboronic acid, followed with the removal of the isopropylidene group to afford the derivatives 7. This strategy will help to construct such fused multicyclic quinazolinone-iminosugars efficiently. Some compounds show certain inhibition against α-glucosidase (saccharomyce cerevisiae).

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A range of 3H-1,2-benzoxaphosphepine 2-oxide aryl derivatives with various substitution patterns at positions 7, 8, or 9 of the scaffold was synthesised in five steps from the commercially available salicylaldehydes. All of the newly obtained compounds were studied for their inhibition potency against carbonic anhydrase (CA) isoforms I, II, IX, and XII. Delightfully, these compounds showed a striking selectivity for the cancer-associated CA IX and XII over the cytosolic CA I and II, whose inhibition may lead to side-effects. Overall, a structure-activity relationship (SAR) revealed that 7- and 8-substituted aryl derivatives were more effective inhibitors of CA IX and XII than 9-substituted derivatives. In addition, the fluorine-containing analogues emerged as the most potent CA IX/XII inhibitors in this series.

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Chemical structures bearing a combination of aggregation-induced emission enhancement (AIEE) and intramolecular charge transfer (ICT) properties attracted the attention of many researchers. Recently, there is an increasing demand to pose tunable AIEE and ICT fluorophores that could present their conformation changes-related emission colors by adjusting the medium polarity. In this study, we designed and synthesized a series of 4-alkoxyphenyl-substituted 1,8-naphthalic anhydride derivatives NAxC using the Suzuki coupling reaction to construct donor-acceptor (D-A)-type fluorophores with alkoxyl substituents of varying carbon chain lengths (x = 1, 2, 4, 6, 12 in NAxC). To explain the observation that molecules with longer carbon chains revealed unusual fluorescence enhancement in water, we study the optical properties and evaluate their locally excited (LE) and ICT states by solvent effects combined with Lippert-Mataga plots. Then, we explored the self-assembly abilities of these molecules in water-organic (W/O) mixed solutions and observed the morphology of its nanostructure using a fluorescence microscope and SEM. The results show that NAxC, x = 4, 6, 12 show different degrees of self-assembly behaviors and corresponding aggregation-induced emission enhancement (AIEE) progresses. At the same time, different nanostructures and corresponding spectral changes can be obtained by adjusting the water ratio in the mixed solution. That is, NAxC compounds present different transitions between LE, ICT and AIEE based on the polarity, water ratio and time changes. We designed NAxC as the structure-activity relationship (SAR) of the surfactant to demonstrate that AIEE comes from the formation of micelle-like nanoaggregates, which causes a restriction of the transfer from the LE state to the ICT state, and micelle formation results in a blue-shift in emission and enhances the intensity in the aggregate state. Among them, NA12C is most likely to form micelles and the most obvious fluorescence enhancement, which will switch over time due to the nano-aggregation transition.

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In this study various of thieno[3,2-d]pyrimidine derivatives have been synthesized by treating different secondary amines through aromatic nucleophilic substitution reaction (SN Ar) followed by Suzuki reaction with aryl and heteroaryl boronic acids. A bis-Suzuki coupling was also performed to generate bis-aryl thienopyrimidine derivatives. The synthesized compounds were screened for the hydrolytic activity of h-NTPdase1, h-NTPdase2, h-NTPdase3, and h-NTPdase8. The compound N-benzyl-N-methyl-7-phenylthieno[3,2-d]pyrimidin-4-amine 3 j selectively inhibits the activity of h-NTPdase1 with IC50 value of 0.62±0.02 µM whereas, the compound 4 d was the most potent inhibitor of h-NTPdase2 with sub-micromolar IC50 value of 0.33±0.09 µM. Similarly, compounds 4 c and 3 b were found to be selective inhibitors for isozymes h-NTPdase3 (IC50 =0.13±0.06 µM) and h-NTPdase8 (IC50 =0.32±0.10 µM), respectively. The molecular docking study of the compounds with the highest potency and selectivity revealed the interactions with the important amino acid residues.

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In the present study, a novel magnetic ethylene-based periodic mesoporous organosilica supported Pd-Schiff base complex (Fe3O4@PMO/SB-Pd) was prepared, characterized and applied as a recoverable nanocatalyst for green synthesis of Suzuki products. Chemical composition, magnetic and thermal behavior, morphology and particle size of Fe3O4@PMO/SB-Pd were investigated by using FT-IR, TGA, EDX, VSM, PXRD, TEM and Scanning electron microscopy (SEM) analyses. The Fe3O4@PMO/SB-Pd nanocomposite was applied as an efficient nanocatalyst in the Suzuki reaction under ultrasonic conditions giving corresponding products in high yield. Some advantages of this study are simple purification of products, the use of water solvent, easy catalyst separation, short reaction time and high catalyst efficiency and recoverability.

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A new eco-friendly catalytic system is devised for C-C bond formation through Suzuki coupling, using an impressive nanocatalyst (Fe3O4/L-(+)-tartaric acid/Pd-NPs). It contains immobilized palladium (0) onto magnetite nanoparticles, stabilized by tartaric acid, and is characterized by FT-IR, XRD, EDS, SEM, TEM, TGA, and VSM. The catalyst is used in an efficient synthesis of biaryls in EtOH/H2O (1:1), in the presence of K2CO3. Our Fe3O4/tartaric acid/Pd-NPs exhibit magnetic recoverability and reusability for five cycles without measurable loss of its activity.

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Quantum-chemical calculations on the spectral properties of some aryl substituted 3-phosphonocoumarins were performed, and the effect of the substituents in the aryl moiety was evaluated. The structures possessing promising fluorescent properties were successfully synthesized via Suzuki and Sonogashira cross-coupling. The synthetic protocol was also applied for the phosphorous chemoisomer of 3-phosphonocoumarin, 1,2-benzoxaphosphorin, and their carboxylate analogues. The optical properties of the arylated and alkynylated products were experimentally determined. The obtained quantum-chemical and experimental results give the possibility for a fine tuning of the optical properties of phosphorous-containing coumarin systems by altering the substituent at its C-6 position.

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The strong radioactivity of iodine compounds derived from nuclear power plant wastes has motivated the development of highly efficient adsorbents. Porous aromatic frameworks (PAFs) have attracted much attention due to their low density and diverse structure. In this work, an azo group containing PAF solid, denoted as LNU-58, was prepared through Suzuki polymerization of tris-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-phenyl)-amine and 3,5-dibromoazobenzene building monomers. Based on the specific polarity properities of the azo groups, the electron-rich aromatic fragments in the hierarchical architecture efficiently capture iodine molecules with an adsorption capacity of 3533.11 mg g-1 (353 wt%) for gaseous iodine and 903.6 mg g-1 (90 wt%) for dissolved iodine. The iodine uptake per specific surface area up to 8.55 wt% m-2 g-1 achieves the highest level among all porous adsorbents. This work illustrates the successful preparation of a new type of porous adsorbent that is expected to be applied in the field of practical iodine adsorption.

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Solar-thermal materials absorb sunlight and convert it into heat, which is released into the surrounding medium. Utilization of solar energy for solvent heating can be a potential method of eco-friendly organic reactions. However, to date, significant heating of the entire volume of a solvent by 1 sun illumination has not been reported. In the present work, a network structure of solar-thermal materials has been proposed for zero energy heating of a solvent under 1 sun illumination. A network-structured solar-thermal material with an additional catalytic function was fabricated by sputtering palladium into a melamine sponge. The nanocrystalline palladium-decorated melamine sponge (Pd-sponge) has excellent sunlight absorption properties in the entire wavelength range that enable efficient solar-thermal conversion. The Pd-sponge can reduce heat loss to the surroundings by effectively blocking thermal radiation from the heated solvent. The temperature of the reaction solution with the ethanol-water mixture filled in the Pd-sponge increased from 23 to 59 °C under 1 sun illumination. The elevated temperature of the reaction solutions by solar-thermal conversion successfully accelerated the heterogeneous Pd-catalyzed Suzuki coupling reactions with high conversions. Easy and low-energy-consuming multicycle use of the solar-thermal and catalytic properties of the Pd-sponge has also been demonstrated.

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Metal N-heterocyclic carbenes (M-NHCs) on the pore walls of a porous metal-organic framework (MOF) can be used as active sites for efficient organic catalysis. Traditional approaches that need strong alkaline reagents or insoluble Ag2O are not, however, suitable for the incorporation of NHCs on the backbones of MOFs because such reagents could destroy their frameworks or result in low reactivity. Accordingly, development of facile strategies toward functional MOFs with covalently bound M-NHCs for catalysis is needed. Herein, we describe the development of a general and facile approach to preparing MOFs with covalently linked active M-NHC (M = Pd, Ir) single-site catalysts by using a soluble Ag salt AgOC(CF3)3 as the source and subsequent transmetalation. The well-defined M-NHC-MOF (M = Pd, Ir) catalysts obtained in this way have shown excellent catalytic activity and stability in Suzuki reactions and hydrogen transfer reactions. This provides a general and facile strategy for anchoring functional M-NHC single-site catalysts onto functionalized MOFs for different reactions.

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A series of novel 7-aryl-7-deazaadenine-based N-branched acyclic nucleoside phosphonates (aza-ANPs) has been prepared using the optimized Suzuki cross-coupling reaction as the key synthetic step. The final free phosphonates 15a-h were inactive, due to their inefficient transport across cell membranes, but they inhibited Trypanosoma brucei adenine phosphoribosyltransferase (TbrAPRT1) with Ki values of 1.7-14.1 µM. The corresponding phosphonodiamidate prodrugs 14a-h exhibited anti-trypanosomal activity in the Trypanosoma brucei brucei cell-based assay with EC50 values in the range of 0.58-6.8 µM. 7-(4-Methoxy)phenyl-7-deazapurine derivative 14h, containing two phosphonate moieties, was the most potent anti-trypanosomal agent from the series, with EC50 = 0.58 µM and SI = 16. Finally, phosphonodiamidate prodrugs 14a-h exerted low micromolar cytotoxicity against leukemia and/or cancer cell lines tested.

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The development of highly efficient adsorptive material for the selective capture of Pd(II), and re-utilization of spent Pd(II)-loaded adsorbent as an efficient catalyst for organic synthesis are of great significance, but challenging. Particularly, the heterogeneous palladium-catalyzed Suzuki reaction in aqueous media is much more challenging than that of homogeneous. Herein, several novel Pd(II) ion-imprinted polymers (PIIPs) based on dendritic fibrous silica particles are constructed by surface ion imprinting technology (SIIT), using Schiff base and pyridine groups functionalized organosilicon as functional monomer. The PIIP-3 prepared by 3 g of functional monomer exhibits the best adsorption performance, and shows ultrafast (10 min) and selective capture of Pd(II) with high uptake capacity (382.5 mg/g). Moreover, the waste Pd(II) loaded PIIP-3 (PIIP-3-Pd) can serve as a catalyst towards the Suzuki reaction in water, affording 94.2 % yield of the desired product. Interestingly, the PIIP-3-Pd can be reused 12 times without an appreciable decrease in catalytic activity, which is probably due to the imprinted cavity and specific recognition site of PIIP-3 can match and recapture Pd active species in a complex catalytic environment. Thus, this work demonstrates huge potentials of SIIT to enhance the selectivity of adsorption process and increase the lifetime of catalysts.

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In this study, a series of N-heterocyclic indolyl ligand precursors 2-Py-Py-IndH, 2-Py-Pz-IndH, 2-Py-7-Py-IndH, 2-Py-7-Pz-IndH, and 2-Ox-7-Py-IndH (L1H-L5H) were prepared. The treatment of ligand precursors with 1 equivalent of palladium acetate affords palladium complexes 1-5. All ligand precursors and palladium complexes were characterized by NMR spectroscopy and elemental analysis. The molecular structures of complexes 3 and 5 were determined by single crystal X-ray diffraction techniques. The application of those palladium complexes 1-5 to the Suzuki reaction with aryl halide substrates was examined.

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Taking the advantage of multifunctional characteristics of chitosan (CS), we have developed new scaffolds (imidazolium-vanillyl-chitosan Schiff bases (IVCSSBs)) for supporting Pd(II) and Ru(II) ions in catalyzing Suzuki coupling reactions. The structures of new materials were described based on their elemental, spectral, thermal, and microscopic analysis. The strong interactions between the binding sites of IVCSSB ligand (OH, H-C=N, and OCH3 groups) and Pd(II) ions resulted in the formation of an excellent heterogeneous catalyst (Pd(II)IVCSSB1) with amazing catalytic activity (up to 99%) and highly stable in the reaction medium. The reusability experiments for Pd(II)IVCSSB1 revealed that there is no appreciable decrease in its catalytic activity even after five consecutive operation runs. Furthermore, this heterogeneous catalyst showed an excellent selectivity toward the cross-coupling reaction where no homo-coupling byproducts were observed in the 1H NMR spectra of the obtained products. Consequently, the present ionic catalytic system may open a new window for a novel generation of ionic bio-based catalysts for organic transformations.

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Suzuki cross-coupling reactions catalyzed by palladium are authoritative protocols in fine-chemical synthesis. Mass transfer and catalyst activity are both significant factors affecting the reaction efficiency in heterogeneous reactions. Although the holistic catalysts hold great promise in heterogeneous reactions due to the enhanced mass transport and convenient recycling, the unsatisfied catalytic activity has impeded further large-scale applications. In addition, another pronounced barrier is the product separation in the intricate system. Here, the catalytic production and separation of biphenyl (purity of 99.7%) were achieved by integrating the Suzuki cross-coupling reactions and the crystallization separation for the first time. A hierarchical-structured impeller with Pd nanoparticles (NPs) loaded on the Ni(OH)2 nanosheets was prepared to catalyze the Suzuki reactions for bromobenzene, which exhibits a high turnover frequency (TOF) value of 25,976 h-1 and a yield of 99.5%. The X-ray absorption fine structure (XAFS) analysis has unveiled that the electron transfer between the Pd NPs and Ni(OH)2 accounts for the greatly enhanced catalytic activity. The findings inspire new insights toward rational engineering of highly efficient holistic catalysts for Suzuki reaction, and the innovative integrated technology offers an avenue for the separation and collection of products.

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We herein report the design and synthesis of small-donor molecules, 2,1,3-benzothiadiazole derivatives (2a-d), by Stille or Suzuki reaction. The synthesized compounds were characterized by spectroscopic and electrochemical methods. The compounds 2a-d absorb the light in a wide range (the UV-green/yellow light (2c)) and emit from green to red/near IR light (2c). Furthermore, these compounds show a narrow energy gap (1.75-2.38 eV), and high Ea values increasing for polymers, which prove their electron-donating nature and semiconductor properties. The measurements were enhanced by theoretical modeling.

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