Heterogeneously catalyzed decarbonylation of thioesters by supported Ni, Pd, or Rh nanoparticle catalysts.

Decarbonylation of thioesters has been actively studied using homogeneous metal catalysts as an attractive approach for synthesizing thioethers, which are widely utilized in various fields, because decarbonylation ideally requires no additives and produces CO as the sole theoretical byproduct. However, heterogeneously catalyzed decarbonylation of thioesters has not been reported to date, despite its importance for the construction of environmentally-friendly and practical catalytic systems. This study demonstrated a heterogeneously catalyzed system for the decarbonylation of various aryl thioesters to produce thioethers and CO by utilizing CeO2- or hydroxyapatite-supported Ni, Pd, or Rh nanoparticle catalysts. The Ni catalysts showed high catalytic activity, while the Pd catalysts possessed excellent functional group tolerance. The Rh catalysts were suitable for the selective decarbonylation of unsymmetrically substituted thioesters.

Nanostructured Manganese Oxides within a Ring-Shaped Polyoxometalate Exhibiting Unusual Oxidation Catalysis.

Nanosized manganese oxides have recently received considerable attention for their synthesis, structures, and potential applications. Although various synthetic methods have been developed, precise synthesis of novel nanostructured manganese oxides are still challenging. In this study, using a structurally defined nanosized cavity inside a ring-shaped polyoxometalate, we succeeded in synthesizing two types of discrete 18 and 20 nuclear nanostructured manganese oxides, Mn18 and Mn20, respectively. In particular, Mn18 showed much higher catalytic activity than other manganese oxides for the oxygenation of alkylarenes including electron-deficient ones, and the reaction proceeded through a unique reaction mechanism due to its unusual manganese oxide structure.

Supported Anionic Gold Nanoparticle Catalysts Modified Using Highly Negatively Charged Multivacant Polyoxometalates.

Although supported anionic gold nanoparticle catalysts have been theoretically investigated for their efficacy in activating O2 in aerobic oxidation reactions, limited studies have been reported due to the difficulty of designing these catalysts. Herein, we developed a feasible method for preparing supported anionic gold nanoparticle catalysts using multivacant lacunary polyoxometalates with high negative charges. We confirmed the strong and robust electronic interaction between gold nanoparticles and multivacant lacunary polyoxometalates, and the electronic states of the supported gold nanoparticle catalysts can be sequentially modulated. Particularly, the catalyst prepared using [SiW9 O34 ]10- acted as an efficient reusable heterogeneous catalyst, showing superior catalytic performance for the oxidative dehydrogenation of piperidone derivatives to the corresponding enaminones and remarkably higher stability than supported gold nanoparticle catalysts without this modification.

Selective Synthesis of Primary Anilines from NH3 and Cyclohexanones by Utilizing Preferential Adsorption of Styrene on the Pd Nanoparticle Surface.

Dehydrogenative aromatization is one of the attractive alternative methods for directly synthesizing primary anilines from NH3 and cyclohexanones. However, the selective synthesis of primary anilines is quite difficult because the desired primary aniline products and the cyclohexanone substrates readily undergo condensation affording the corresponding imines (i.e., N-cyclohexylidene-anilines), followed by hydrogenation to produce N-cyclohexylanilines as the major products. In this study, primary anilines were selectively synthesized in the presence of supported Pd nanoparticle catalysts (e.g., Pd/HAP, HAP=hydroxyapatite, Ca10 (PO4 )6 (OH)2 ) by utilizing competitive adsorption unique to heterogeneous catalysis; in other words, when styrene was used as a hydrogen acceptor, which preferentially adsorbs on the Pd nanoparticle surface in the presence of N-cyclohexylidene-anilines, various structurally diverse primary anilines were selectively synthesized from readily accessible NH3 and cyclohexanones. The Pd/HAP catalyst was reused several times though its catalytic performance gradually declined.

Methyl-Selective α-Oxygenation of Tertiary Amines to Formamides by Employing Copper/Moderately Hindered Nitroxyl Radical (DMN-AZADO or 1-Me-AZADO).

Methyl-selective α-oxygenation of tertiary amines is a highly attractive approach for synthesizing formamides while preserving the amine substrate skeletons. Therefore, the development of efficient catalysts that can advance regioselective α-oxygenation at the N-methyl positions using molecular oxygen (O2 ) as the terminal oxidant is an important subject. In this study, we successfully developed a highly regioselective and efficient aerobic methyl-selective α-oxygenation of tertiary amines by employing a Cu/nitroxyl radical catalyst system. The use of moderately hindered nitroxyl radicals, such as 1,5-dimethyl-9-azanoradamantane N-oxyl (DMN-AZADO) and 1-methyl-2-azaadamanane N-oxyl (1-Me-AZADO), was very important to promote the oxygenation effectively mainly because these N-oxyls have longer life-times than less hindered N-oxyls. Various types of tertiary N-methylamines were selectively converted to the corresponding formamides. A plausible reaction mechanism is also discussed on the basis of experimental evidence, together with DFT calculations. The high regioselectivity of this catalyst system stems from steric restriction of the amine-N-oxyl interactions.

Supported Gold Nanoparticles for Efficient α-Oxygenation of Secondary and Tertiary Amines into Amides.

Although the α-oxygenation of amines is a highly attractive method for the synthesis of amides, efficient catalysts suited to a wide range of secondary and tertiary alkyl amines using O2 as the terminal oxidant have no precedent. This report describes a novel, green α-oxygenation of a wide range of linear and cyclic secondary and tertiary amines mediated by gold nanoparticles supported on alumina (Au/Al2 O3 ). The observed catalysis was truly heterogeneous, and the catalyst could be reused. The present α-oxygenation utilizes O2 as the terminal oxidant and water as the oxygen atom source of amides. The method generates water as the only theoretical by-product, which highlights the environmentally benign nature of the present reaction. Additionally, the present α-oxygenation provides a convenient method for the synthesis of (18) O-labeled amides using H2 (18) O as the oxygen source.

Gold Nanoparticles Supported on a Layered Double Hydroxide as Efficient Catalysts for the One-Pot Synthesis of Flavones.

Flavones are a class of natural products with diverse biological activities and have frequently been synthesized by step-by-step procedures using stoichiometric amounts of reagents. Herein, a catalytic one-pot procedure for the synthesis of flavone and its derivatives is developed. In the presence of gold nanoparticles supported on a Mg-Al layered double hydroxide (Au/LDH), various kinds of flavones can be synthesized starting from 2'-hydroxyacetophenones and benzaldehydes (or benzyl alcohols). The present one-pot procedure consists of a sequence of several reactions, and Au/LDH can catalyze all these different types of reactions. The catalysis is shown to be truly heterogeneous, and Au/LDH can be readily recovered and reused.

Multidentate polyoxometalate modification of metal nanoparticles with tunable electronic states.

To respond to the increasing demands for practical applications, stabilization and property modulation of metal nanoparticles have emerged as a key research subject. Herein, we present a viable protocol for preparing small metal nanoparticles (<5 nm; Ag, Pd, Pt, and Ru) via multidentate polyoxometalate (POM, [SiW9O34]10-) modification. In addition to enhancing stability, the POMs can modulate the electronic states of metal nanoparticles. Moreover, immobilization of the POM-modified metal nanoparticles on solid supports enables further tuning of the electronic states via a cooperative effect between the POMs and the supports without altering the particle size. Notably, POM-modified Pd nanoparticles on carbon support exhibited superior catalytic activity and selectivity in hydrogenation reactions in comparison with the catalyst without the POM modification.

Heterogeneously catalyzed thioether metathesis by a supported Au-Pd alloy nanoparticle design based on Pd ensemble control.

C-S bond metathesis of thioethers has gained attention as a new approach to the late-stage diversification of already existing useful thioethers with molecular frameworks intact. However, direct or indirect thioether metathesis is scarcely reported, and heterogeneously catalyzed systems have not been explored. Here, we develop heterogeneously catalyzed direct thioether metathesis using a supported Au-Pd alloy nanoparticle catalyst with a high Au/Pd ratio. The Au-diluted Pd ensembles suppress the strong π-adsorption of diaryl thioethers on the nanoparticles and promote transmetalation via thiolate spill-over onto neighboring Au species, enabling an efficient direct thioether metathesis.

Photocatalytic aerobic α-oxygenation of amides to imides using a highly durable decatungstate tetraphenylphosphonium salt.

Decatungstate is a potent photocatalyst for hydrogen atom transfer (HAT) but faces degradation issues when using a typical tetra-n-butylammonium salt. Herein, we employed tetraphenylphosphonium as a countercation to yield a highly durable and efficient HAT photocatalyst, enabling α-oxygenation of amides to their corresponding imides using O2 as an oxidant.

Ultra-stable and highly reactive colloidal gold nanoparticle catalysts protected using multi-dentate metal oxide nanoclusters.

Owing to their remarkable properties, gold nanoparticles are applied in diverse fields, including catalysis, electronics, energy conversion and sensors. However, for catalytic applications of colloidal gold nanoparticles, the trade-off between their reactivity and stability is a significant concern. Here we report a universal approach for preparing stable and reactive colloidal small (~3 nm) gold nanoparticles by using multi-dentate polyoxometalates as protecting agents in non-polar solvents. These nanoparticles exhibit exceptional stability even under conditions of high concentration, long-term storage, heating and addition of bases. Moreover, they display excellent catalytic performance in various oxidation reactions of organic substrates using molecular oxygen as the sole oxidant. Our findings highlight the ability of inorganic multi-dentate ligands with structural stability and robust steric and electronic effects to confer stability and reactivity upon gold nanoparticles. This approach can be extended to prepare metal nanoparticles other than gold, enabling the design of novel nanomaterials with promising applications.

Heterogeneously Catalyzed Selective Acceptorless Dehydrogenative Aromatization to Primary Anilines from Ammonia via Concerted Catalysis and Adsorption Control.

Although catalytic dehydrogenative aromatization from cyclohexanones and NH3 is an attractive synthetic method for primary anilines, using a hydrogen acceptor was indispensable to achieve satisfactory levels of selectivity in liquid-phase organic synthetic systems without photoirradiation. In this study, we developed a highly selective synthesis of primary anilines from cyclohexanones and NH3 via efficient acceptorless dehydrogenative aromatization heterogeneously catalyzed by an Mg(OH)2-supported Pd nanoparticle catalyst in which Mg(OH)2 species are also deposited on the Pd surface. The basic sites of the Mg(OH)2 support effectively accelerate the acceptorless dehydrogenative aromatization via concerted catalysis, suppressing the formation of secondary amine byproducts. In addition, the deposition of Mg(OH)2 species inhibits the adsorption of cyclohexanones on the Pd nanoparticles to suppress phenol formation, achieving the desired primary anilines with high selectivity.

Regiospecific α-methylene functionalisation of tertiary amines with alkynes via Au-catalysed concerted one-proton/two-electron transfer to O2.

Regioselective transformations of tertiary amines, which are ubiquitously present in natural products and drugs, are important for the development of novel medicines. In particular, the oxidative α-C-H functionalisation of tertiary amines with nucleophiles via iminium cations is a promising approach because, theoretically, there is almost no limit to the type of amine and functionalisation. However, most of the reports on oxidative α-C-H functionalisations are limited to α-methyl-selective or non-selective reactions, despite the frequent appearance of α-methylene-substituted amines in pharmaceutical fields. Herein, we develop an unusual oxidative regiospecific α-methylene functionalisation of structurally diverse tertiary amines with alkynes to synthesise various propargylic amines using a catalyst comprising Zn salts and hydroxyapatite-supported Au nanoparticles. Thorough experimental investigations suggest that the unusual α-methylene regiospecificity is probably due to a concerted one-proton/two-electron transfer from amines to O2 on the Au nanoparticle catalyst, which paves the way to other α-methylene-specific functionalisations.

C-H Bond Activation Mechanism by a Pd(II)-(µ-O)-Au(0) Structure Unique to Heterogeneous Catalysts.

We focused on identifying a catalytic active site structure at the atomic level and elucidating the mechanism at the elementary reaction level of liquid-phase organic reactions with a heterogeneous catalyst. In this study, we experimentally and computationally investigated efficient C-H bond activation for the selective aerobic α,ß-dehydrogenation of saturated ketones by using a Pd-Au bimetallic nanoparticle catalyst supported on CeO2 (Pd/Au/CeO2) as a case study. Detailed characterization of the catalyst with various observation methods revealed that bimetallic nanoparticles formed on the CeO2 support with an average size of about 2.5 nm and comprised a Au nanoparticle core and PdO nanospecies dispersed on the core. The formation mechanism of the nanoparticles was clarified through using several CeO2-supported controlled catalysts. Activity tests and detailed characterizations demonstrated that the dehydrogenation activity increased with the coordination numbers of Pd-O species in the presence of Au(0) species. Such experimental evidence suggests that a Pd(II)-(µ-O)-Au(0) structure is the true active site for this reaction. Based on density functional theory calculations using a suitable Pd1O2Au12 cluster model with the Pd(II)-(µ-O)-Au(0) structure, we propose a C-H bond activation mechanism via concerted catalysis in which the Pd atom acts as a Lewis acid and the adjacent µ-oxo species acts as a Brønsted base simultaneously. The calculated results reproduced the experimental results for the selective formation of 2-cyclohexen-1-one from cyclohexanone without forming phenol, the regioselectivity of the reaction, the turnover-limiting step, and the activation energy.

Selective primary aniline synthesis through supported Pd-catalyzed acceptorless dehydrogenative aromatization by utilizing hydrazine.

By utilizing hydrazine (N2H4) as the nitrogen source in the presence of a hydroxyapatite-supported Pd nanoparticle catalyst (Pd/HAP), various primary anilines can be selectively synthesized from cyclohexanones via acceptorless dehydrogenative aromatization. The strong nucleophilicity of N2H4 and the stability of the hydrazone intermediates can effectively suppress the formation of the undesired secondary aniline byproducts.

Heterogeneously Ni-Pd nanoparticle-catalyzed base-free formal C-S bond metathesis of thiols.

This study rationally designed a heterogeneously catalyzed system (i.e., using Ni-Pd alloy nanoparticles supported on hydroxyapatite (Ni-Pd/HAP) under an H2 atmosphere) achieving an efficient base-free formal C-S bond metathesis of various thiols via suppression of the Ni catalysis deactivation.

Synthesis of unsymmetrically substituted triarylamines via acceptorless dehydrogenative aromatization using a Pd/C and p-toluenesulfonic acid hybrid relay catalyst.

An efficient and convenient procedure for synthesizing triarylamines based on a dehydrogenative aromatization strategy has been developed. A hybrid relay catalyst comprising carbon-supported Pd (Pd/C) and p-toluenesulfonic acid (TsOH) was found to be effective for synthesizing a variety of triarylamines bearing different aryl groups starting from arylamines (diarylamines or anilines), using cyclohexanones as the arylation sources under acceptorless conditions with the release of gaseous H2. The proposed reaction comprises the following relay steps: condensation of arylamines and cyclohexanones to produce imines or enamines, dehydrogenative aromatization of the imines or enamines over Pd nanoparticles (NPs), and elimination of H2 from the Pd NPs. In this study, an interesting finding was obtained indicating that TsOH may promote the dehydrogenation.

Gold nanoparticles on OMS-2 for heterogeneously catalyzed aerobic oxidative α,ß-dehydrogenation of ß-heteroatom-substituted ketones.

In the presence of Au nanoparticles supported on manganese oxide OMS-2 (Au/OMS-2), various kinds of ß-heteroatom-substituted α,ß-unsaturated ketones (heteroatom = N, O, S) can be synthesized through α,ß-dehydrogenation of the corresponding saturated ketones using O2 (in air) as the oxidant. The catalysis of Au/OMS-2 is truly heterogeneous, and the catalyst can be reused.