Chemoselective Catalyst Research Articles

Cyclopropenium Sulfide as Lewis Base Catalyst for Chemoselective and Regioselective Electrophilic Selenylation of Phenols

Cyclopropenium Sulfide as Lewis Base Catalyst for Chemoselective and Regioselective Electrophilic Selenylation of Phenols

Fe3O4@SiO2@SBA-3@CPTMS@Arg-Cu: preparation, characterization, and catalytic performance in the conversion of nitriles to amides and the synthesis of 5-substituted 1H-tetrazoles.

A novel, efficient, and recyclable mesoporous Fe3O4@SiO2@SBA-3@CPTMS@Arg-Cu nanocatalyst was synthesized by grafting l-arginine (with the ability to coordinate with Cu) onto a mixed phase of a magnetic mesoporous SBA-3 support. The catalyst was characterized using several techniques, including Fourier-transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA), vibrating sample magnetometry (VSM), X-ray diffraction (XRD) analysis, N2 adsorption-desorption analysis, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray (EDX) analysis, and atomic absorption spectroscopy (AAS). The resulting solid material possessed a surface area of 145 m2 g-1 and a total pore volume of 34 cm3 g-1. The prepared mesoporous material was studied as a practical, recyclable, and chemoselective catalyst in some organic functional group transformations such as the conversion of nitriles to amides and synthesis of 5-substituted 1H-tetrazoles. This novel magnetic nanocatalyst proved to be effective and provided the products in high to excellent yields under green solvent conditions. Meanwhile, the as-prepared Fe3O4@SiO2@SBA-3@CPTMS@Arg-Cu demonstrated excellent reusability and stability under reaction conditions, and its catalytic activity shown only a slight decrease after seven consecutive runs. Therefore, the as-synthesized magnetic Fe3O4@SiO2@SBA-3@CPTMS@Arg-Cu has broad prospects for practical applications, and offers various benefits such as simplicity, nontoxicity, low cost, simple work-up, and an environmentally benign nature.

Hydrogenation of CO2 by a Bifunctional PC(sp3 )P Iridium(III) Pincer Complex Equipped with Tertiary Amine as a Functional Group.

Reversible hydrogen storage in the form of stable and mostly harmless chemical substances such as formic acid (FA) is a cornerstone of a fossil fuels-free economy. In the past, we have reported a primary amine-functionalized bifunctional iridium(III)-PC(sp3 )P pincer complex as a mild and chemoselective catalyst for the additive-free decomposition of neat formic acid. In this manuscript, we report on the successful application of a redesigned complex bearing tertiary amine functionality as a catalyst for mild hydrogenation of CO2 to formic acid. The catalyst demonstrates TON up to 6×104 and TOF up to 1.7×104 h-1 . In addition to the practical value of the catalyst, experimental and computational mechanistic studies provide the rationale for the design of improved next-generation catalysts.

Iodine-Mediated Oxidative Annulation of β,γ-Unsaturated Hydrazones in Dimethyl Sulfoxide: A Strategy to Build 1,6-Dihydropyridazines and Pyrroles.

Simple, commercially available iodine was successfully employed as a highly efficient and chemoselective catalyst for the oxidative annulation of β,γ-unsaturated hydrazones to produce 1,6-dihydropyridazines under mild conditions for the first time. Interestingly, when active β,γ-unsaturated hydrazone compounds containing electron-donating groups, such as furyl, thienyl, and cycloalkyl, were used, pyrroles were obtained. A gram-scale preparation experiment and further derivatization of pyridazines demonstrated the potential applicability of our synthesis method. Experimental studies and density functional theory calculations unveiled the origin of the chemoselectivity determining the formation of different products.

Highly Chemoselective Zn+2 -Catalyzed Hydrosilylation of Alkynes.

Hydrosilylation of C=C double and C≡C triple bonds is one of the most widely used processes in organosilicon chemistry, mostly catalyzed by Pt-based complexes. Herein, the synthesis of a dicationic Zn+2 -based complex with a tripodal tris(2-pyridylmethyl)amine (TPA) ligand is reported which was found to be a highly chemoselective catalyst for hydrosilylation reactions of alkynes. Mechanistic studies revealed that unlike typical Zn-catalyzed hydrosilylation reactions where the key step is the activation of the Si-H bond, this system catalyzes the hydrosilylation reaction through the activation of C≡C triple bonds, which presumably is the reason for its high chemoselectivity. Remarkably, the hydrosilylation of alkynes could be performed in the presence of alkenes and other functional groups that remained intact in this reaction.

Electron-Poor Phosphines Enable the Selective Semihydrogenation Reaction of Alkynes with Pd on Carbon Catalysts.

An alternative to the Lindlar catalyst for the semihydrogenation reaction of alkynes to alkenes is of high interest. Here we show that palladium on carbon (Pd/C), i.e., a widely available supported Pd catalyst, is converted from an unselective to a chemoselective catalyst during the semihydrogenation reaction of alkynes, after the addition of catalytic amounts of commercially available electron-poor phosphines. The catalytic activity is ≤7 times greater, and the selectivity is comparable to that of the industrial benchmark Lindlar catalyst.

Nanostructured Functionalised Niobium Oxide as Chemoselective Catalyst for Acetalation of Glucose

Nanostructured Functionalised Niobium Oxide as Chemoselective Catalyst for Acetalation of Glucose

“On-water” reduction of α-keto amide by Hantzsch ester: A chemoselective catalyst- and additive-free way to α-hydroxy amide

An efficient and practical method for chemoselective “on-water” reduction of α-keto amide by Hantzsch ester without using any catalysts and additives was developed. Control experiments indicated that the intramolecular hydrogen bond of α-keto amide was crucial for this transformation. A variety of α-hydroxy amides were prepared in high yields in an environmentally friendly way.

ZnBr2-Catalyzed Dehydrogenative Borylation of Terminal Alkynes.

The simple, commercially available ZnBr2 has been successfully employed as a highly efficient and chemoselective catalyst for the dehydrogenative borylation of terminal alkynes with HBpin under mild conditions. It shows a good tolerance toward various functional groups such as aryl, alkyl, heteroaryl, etc. The plausible reaction mechanism has been investigated based on the corresponding stoichiometric experiments and DFT calculations.

Fabrication of Pd/Mg2 P2 O7 via a Struvite-Template Way from Wastewater and Application as Chemoselective Catalyst in Hydrogenation of Nitroarenes.

A highly efficient heterogeneous catalyst Pd/Mg2 P2 O7 was fabricated by combining palladium nanoparticles (PdNPs) and mesoporous Mg2 P2 O7 fibers/rods. Mg2 P2 O7 fibers with ultra-high specific surface area were prepared from struvite as templates, which were synthesized from waste water containing N- and P-containing pollutants. This strategy provided a novel pathway for developing advanced catalysts from eutrophication-polluted water. The composite Pd/Mg2 P2 O7 showed brilliant performance in selective hydrogenation of nitro aromatics to give anilines. As an example of nitrobenzene hydrogenation, the conversion to aniline and selectivity were found to reach almost 100 % at a temperature of T=90 °C and under a pressure of P =2.0 MPa. The superior performance was found to originate from PdNPs, which were boosted by electron transfer afforded by the nanofiber Mg2 P2 O7 supports. The favorable adsorption of withdrawing groups (-NO2 ) was realized by synergistic effects between Pd and oxygen vacancies provided by pyrolysis of struvite. The catalyst remained stable after cycles of reuse with little degradation in catalytic performance.

Influence of Brønsted acid sites on chemoselective synthesis of pyrrolidones over H-ZSM-5 supported copper catalyst

Cu(0)/H-ZSM-5 was identified as a chemoselective catalyst in the reductive amination of levulinic acid for the synthesis of pyrrolidones at ambient pressure and in aqueous media. The chemoselective nature of Cu was explained by carbonyl interaction with surface Brønsted acid sites deduced by pyridine and acetone adsorbed in situ infrared (IR) spectroscopic studies in conjunction with N2O titration. A strong polarization of band at 1685 cm−1 and an increase in its intensity with a decrease in Si/Al ratio of the H-ZSM-5 was found to be a key factor in the reductive amination activity. Structure activity relationship was established using the physicochemical characteristics of the catalysts analyzed by XRD, BET-SA, H2-TPR, NH3-TPD and XPS analyses.

Gold-like Thiolate-Protected Ultrasmall Cubic Copper Nanocluster-Based Metal-Organic Framework as a Selective Catalyst for Stepwise Synthesis of Unsymmetric Bistriazole by Click Reaction.

We report a facile synthesis of a thiolate-protected water-soluble ultrasmall cubic copper nanocluster-based metal-organic framework (CuMOF) as an efficient and chemoselective catalyst for the azide-alkyne click reaction. Interestingly, the diffuse reflectance spectra of CuMOFs exhibit three discrete plasmon bands at 463, 505, and 674 nm, which are similar to those corresponding to the fingerprint region of thiolate-protected atomically precise Au25 nanoclusters; hence, CuMOFs are termed as gold-like ultrasmall cubic copper nanoclusters. The high-resolution transmission electron microscopy (HRTEM) and powder X-ray diffraction (XRD) patterns confirm the cubic morphology of CuMOFs with nanoclusters showing particle size distribution of ∼2-12 nm. The matrix-assisted laser desorption ionization (MALDI) spectrum of CuMOFs is attributed to the individual particles consisting of few Cun(SR)m with Cu(0) core atoms and Cu(I)SR staples, i.e., Cu2(SR)4, Cu(SR)6, Cu3(SR)7, and Cu4(SR)8. To our surprise, the unsymmetric bistriazoles resulting from the click reaction of bifunctional azides and alkynes in the presence of CuMOFs were achieved by step-by-step conversion of the terminal azide selectively with maximum yield in the range of 70-88%. The nitrogen adsorption-desorption studies confirm the size-dependent surface area, pore volume, and pore size for the CuMOFs prepared by varying metal-to-ligand ratios. The plausible mechanism for the selective mono-click at CuMOFs suggests the existence of bifunctional terminal interactions via thiol and sulfonate groups that might have provided the site-isolation-based active sites for selective catalysis. The easy recovery of CuMOFs and their reusability up to 5 times without significant loss of activity are very promising for the selective organic conversions in pharmaceutical and industrial formulations.

Glycerol Boosted Rh-Catalyzed Hydroaminomethylation Reaction: A Mechanistic Insight.

We report a Rh-catalyzed hydroaminomethylation reaction of terminal alkenes in glycerol that proceeds efficiently under mild conditions to produce the corresponding amines in relatively high selectivity towards linear amines, moderate to excellent yields by using a low catalyst loading (1 mol % [Rh], 2 mol % phosphine) and relative low pressure (H2 /CO, 1:1, total pressure 10 bar). This work sheds light on the importance of glycerol in enabling enamine reduction via hydrogen transfer. Moreover, evidence for the crucial role of Rh as chemoselective catalyst in the condensation step has been obtained for the first time in the frame of the hydroaminomethylation reaction by precluding deleterious aldol condensation reactions. The hydroaminomethylation proceeds under a molecular regime; the outcome of catalytically active species into metal-based nanoparticles renders the catalytic system inactive.

MOF-derived AgCo alloy nanoparticle protected by mesoporous carbon as chemoselective catalyst for hydrogenation of citral

A new robust AgCo alloy catalyst which presents as clean uniform bimetallic nanoparticles (NPs) protected by a mesoporous carbon layer was feasibly produced from a controllable pyrolysis strategy of metal-organic frameworks (MOFs) precursor. The pyrolysis destroyed the microporous structure of Ag(I)-doped Co-MOF but generated a new mesoporous carbon layer, which led to effective substrates diffusion and in situ reduction and generation of the highly active alloy nanoparticles. Benefited from the well dispersed bimetallic alloy NPs and the interaction with Ag and Co, which can adjust the electron distribution on the catalyst surface, the as-prepared AgCo alloy catalyst delivered remarkably selective hydrogenation activity of citral with nearly full conversion and 70% selectivity for hydrogenation of citral to nerol and geraniol under the optimum reaction conditions, which is comparable to the reported Pt, Ru and Re catalysts. In addition, since the AgCo alloy NPs were well protected from aggregation and leaching by the mesoporous carbon, the magnetic catalyst exhibited extremely high catalytic recyclability without any decrease of conversion and selectivity after ten cycles of reuse.

Au Nanoparticles Confined in SBA-15 as a Highly Efficient and Stable Catalyst for Hydrogenation of Quinoline to 1,2,3,4-Tetrahydroquinoline

Au nanoparticles confined within the mesopores of the modified SBA-15 were obtained through adsorption-reduction method and firstly employed as chemoselective catalyst for quinoline hydrogenation. The effects of Au loadings, calcination temperature as well as structure of support on catalytic performances of Au catalysts were explored. The as-obtained 1.2%Au@SBA-15-500 catalyst exhibited high activity, excellent selectivity towards 1,2,3,4-tetrahydroquinoline and extraordinary sintering-resistant property as high as 800 °C, which is sharp contrast to the 1.3%Au/SiO2-500 catalyst. It also showed good recyclability and versatility for quinoline derivatives. The observed properties were assigned to small-sized Au nanoparticles and mesopores of SBA-15. Our work provides a facile and promising approach to construct metal nanocatalysts with high catalytic performance by the use of mesoporous materials.

The synthesis and structure of pyridine-oxadiazole iridium complexes and catalytic applications: Non-coordinating-anion-tuned selective C[sbnd]N bond formation

Several novel pyridine-oxadiazole iridium complexes were synthesized and characterized through X-ray crystallography. The designed iridium complexes revealed surprisingly high catalytic activity in CN bondformation of amides and benzyl alcohols with the assistance of non-coordinating anions. In an attempt to achieve borrowing hydrogen reactions of amides with benzyl alcohols, N,N'-(phenylmethylene)dibenzamide products were unexpectedly isolated under non-coordinating anion conditions, whereas N-benzylbenzamide products were achieved in the absence of non-coordinating anions. The mechanism explorations excluded the possibility of "silver effect" (silver-assisted or bimetallic catalysis) and revealed that the reactivity of iridium catalyst was varied by non-coordinating anions. This work provided a convenient and useful methodology that allowed the iridium complex to be a chemoselective catalyst and demonstrated the first example of non-coordinating-anion-tuned selective CN bond formation

Nickamine and Analogous Nickel Pincer Catalysts for Cross-Coupling of Alkyl Halides and Hydrosilylation of Alkenes.

Ligand development plays an essential role in the advance of homogeneous catalysis. Tridentate, meridionally coordinating ligands, commonly termed pincer ligands, have been established as a privileged class of ligands in catalysis because they confer high stability while maintaining electronic tenability to the resulting metal complexes. Pincer ligands containing "soft" donors such as phosphines are typically used for late transition-metal ions, which are considered "soft" acids. Driven by our interest to develop base-metal catalysis and in view of the "hard" character of base-metal ions, our group explored a pincer ligand containing only "hard" nitrogen donors. A prototypical nickel complex of this ligand, "Nickamine", turned out to be an efficient catalyst in a wide range of organic reactions. Because of its propensity to mediate single-electron redox chemistry, Nickamine is particularly suited to catalyze cross-coupling of nonactivated alkyl halides through radical pathways. These coupling partners have been challenging substrates for traditional, palladium-based catalysts because of difficult oxidative addition and nonproductive β-H elimination. The high activity of Nickamine for cross-coupling leads to high chemoselectivity and functional group tolerance, even when reactive Grignard reagents are employed as nucleophiles. The scope of the catalysis is broad and encompasses sp3-sp3, sp3-sp2, and sp3-sp cross-coupling. The defined nature of Nickamine facilitated the mechanistic study of cross-coupling reactions. Experiments involving radical-probe substrates, presumed intermediates and dormant species, kinetics, and density functional theory computations revealed a bimetallic oxidative addition pathway. In this pathway, two Ni centers each provide one electron to support the two-electron activation of an alkyl halide substrate. The success of Nickamine motivated our systematic structure-activity studies aiming at improved activity in certain reactions through ligand modification. Indeed, better catalysts have been developed for cross-coupling of secondary alkyl halides as well as direct alkynylation of alkyl halides. The improvement is attributed to a more accessible Ni center in the new catalysts than in Nickamine. Surprisingly, the improvement could be obtained simply by replacing a dimethyl amino group in Nickamine with a pyrrolidino group. During the study of the catalytic cycle of Nickamine in cross-coupling reactions, we synthesized the corresponding Ni-H species. Consequently, we explored the catalytic application of Nickamine in Ni-H mediated reactions, such as hydrosilylation. To our delight, Nickamine is a chemoselective catalyst for hydrosilylation of alkenes while tolerating a reactive C=O group. An analogous Ni pincer complex was found to catalyze unusual hydrosilylation reactions using alkoxy hydrosilanes as surrogates of gaseous silanes.

Catalytic Generation and Chemoselective Transfer of Nucleophilic Hydrides from Dihydrogen

Copper(I)-N-heterocyclic-carbene (NHC) complexes enabled the catalytic generation of nucleophilic hydrides from dihydrogen (H2 ) and their subsequent transfer to allylic chlorides. The highly chemoselective catalyst displayed no concomitant hydrogenation reactivity; in fact, the terminal double bond formed in the hydride transfer remained intact. Switching to deuterium gas (D2 ) allowed for regioselective monodeuteration with excellent isotope incorporation.

Pd nanoparticles supported on a covalent triazine-based framework material: an efficient and highly chemoselective catalyst for the reduction of nitroarenes

Well-dispersed Pd nanoparticles supported on a triazine-based framework were prepared and the material displayed excellent catalytic activity for the transfer hydrogenation of nitroarenes.

Rhenium-Loaded TiO2 : A Highly Versatile and Chemoselective Catalyst for the Hydrogenation of Carboxylic Acid Derivatives and the N-Methylation of Amines Using H2 and CO2.

Herein, we report a heterogeneous TiO2 -supported Re catalyst (Re/TiO2 ) that promotes various selective hydrogenation reactions, which includes the hydrogenation of esters to alcohols, the hydrogenation of amides to amines, and the N-methylation of amines, by using H2 and CO2 . Initially, Re/TiO2 was evaluated in the context of the selective hydrogenation of 3-phenylpropionic acid methyl ester to afford 3-phenylpropanol (pH2 =5 MPa, T=180 °C), which revealed a superior performance over other catalysts that we tested in this study. In contrast to other typical heterogeneous catalysts, hydrogenation reactions with Re/TiO2 did not produce dearomatized byproducts. DFT studies suggested that the high selectivity for the formation of alcohols in favor of the hydrogenation of aromatic rings is ascribed to the higher affinity of Re towards the COOCH3 group than to the benzene ring. Moreover, Re/TiO2 showed a wide substrate scope for the hydrogenation reaction (19 examples). Subsequently, this Re/TiO2 catalyst was applied to the hydrogenation of amides, the N-methylation of amines, and the N-alkylation of amines with carboxylic acids or esters.