Palladium on Carbon-Catalyzed Silane-Reduction of Tertiary Carboxamides: Soluble Palladium Colloids are an Active Catalyst Species

Hosokawa, Satomi; Teramoto, Kazusue; Motoyama, Yukihiro

doi:10.1002/slct.201600552

Cited by 9 publications

(4 citation statements)

References 79 publications

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“…Figure S1B also shows high-resolution XPS of Pd primarily in the Pd(0) state when it is in the nanoparticle state anchored to the HN. It has previously been reported that tertiary amines act as good coordination sites for Pd nanoparticles. ,,,,− Thus, we hypothesize that coordination forces (similar to those observed with transition metal ligands) along with physical entrapment allow the Pd nanoparticles to attach to the polymeric support.…”

Section: Experimental Methodsmentioning

confidence: 62%

“…It has previously been reported that tertiary amines act as good coordination sites for Pd nanoparticles. 28 , 30 , 36 , 37 , 50 − 52 Thus, we hypothesize that coordination forces (similar to those observed with transition metal ligands) along with physical entrapment allow the Pd nanoparticles to attach to the polymeric support.…”

Section: Experimental Methodsmentioning

confidence: 77%

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Continuous Ligand-Free Catalysis Using a Hybrid Polymer Network Support

Davis

Genzer

Efimenko

et al. 2023

JACS Au

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Although the pharmaceutical and fine chemical industries primarily utilize batch homogeneous reactions to carry out chemical transformations, emerging platforms seek to improve existing shortcomings by designing effective heterogeneous catalysis systems in continuous flow reactors. In this work, we present a versatile network-supported palladium (Pd) catalyst using a hybrid polymer of poly(methylvinylether-alt-maleic anhydride) and branched polyethyleneimine for intensified continuous flow synthesis of complex organic compounds via heterogeneous Suzuki–Miyaura cross-coupling and nitroarene hydrogenation reactions. The hydrophilicity of the hybrid polymer network facilitates the reagent mass transfer throughout the bulk of the catalyst particles. Through rapid automated exploration of the continuous and discrete parameters, as well as substrate scope screening, we identified optimal hybrid network-supported Pd catalyst composition and process parameters for Suzuki–Miyaura cross-coupling reactions of aryl bromides with steady-state yields up to 92% with a nominal residence time of 20 min. The developed heterogeneous catalytic system exhibits high activity and mechanical stability with no detectable Pd leaching at reaction temperatures up to 95 °C. Additionally, the versatility of the hybrid network-supported Pd catalyst is demonstrated by successfully performing continuous nitroarene hydrogenation with short residence times (<5 min) at room temperature. Room temperature hydrogenation yields of >99% were achieved in under 2 min nominal residence times with no leaching and catalyst deactivation for more than 20 h continuous time on stream. This catalytic system shows its industrial utility with significantly improved reaction yields of challenging substrates and its utility of environmentally-friendly solvent mixtures, high reusability, scalable and cost-effective synthesis, and multi-reaction successes.

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Section: Experimental Methodsmentioning

confidence: 62%

Section: Experimental Methodsmentioning

confidence: 77%

Continuous Ligand-Free Catalysis Using a Hybrid Polymer Network Support

Davis

Genzer

Efimenko

et al. 2023

JACS Au

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“…We have recently reported that the combination of 1,1,3,3‐tetramethyldisiloxane (TMDS) and commercially available palladium on carbon (Pd/C) was effective catalyst system for the reduction of tertiary carboxamides to amines . In that case, the reaction of carboxylic esters did not proceed leading to the selective formation of amino esters from amido esters.…”

Section: Methodsmentioning

confidence: 99%

Catalytic Silane‐Reduction of Carboxylic Esters and Lactones: Selective Synthetic Methods to Aldehydes, Lactols, and Ethers via Silyl Acetal Intermediates

et al. 2018

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Practical procedures for the production of aldehydes, lactols, and ethers are offered by the palladium‐catalyzed silane‐reduction of carboxylic esters and lactones. The partial reduction of carboxylic esters or lactones with 1,1,3,3‐tetramethyldisiloxane in the presence of commercially available palladium on carbon (Pd/C) and some copper compounds as a co‐catalyst smoothly proceeds under mild conditions to afford the silyl acetal derivatives in high yields, which are easily converted to the corresponding aldehydes or lactols by hydrolysis of silyloxy group. On the other hand, deoxygenated ethers are obtained with high selectivity by treatment of silyl acetals with catalytic amounts of Me3SiOTf at –78 °C or stoichiometric amounts of BF3•OEt2 at ambient temperature.

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“…In electrochemical biosensors, noble metals such as platinum (Pt) and palladium (Pd) are attractive candidates to replace enzymes because of their intrinsic stability and catalytic activity . Metal morphology has been studied extensively because shape is regarded as an influential factor for enhancing activity and stability .…”

Section: Introductionmentioning

confidence: 99%

Fabrication of Shape‐Controlled Palladium Nanoparticle‐Decorated Electrospun Polypyrrole/Polyacrylonitrile Nanofibers for Hydrogen Peroxide Coalescing Detection

Kim

Shin

Jun

et al. 2017

Adv Materials Inter

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Shape‐controlled palladium nanoparticle‐decorated electrospun polypyrrole/polyacrylonitrile nanofibers (Pd_PPy/PAN NFs) are fabricated by electrospinning, vapor deposition polymerization (VDP), and electrodeposition. The electrospun PAN NFs are used as the framework for a composite nanomaterial. To make the material electrically conductive, the framework is coated with PPy by VDP. As‐prepared PPy/PAN NFs are used as the working electrode during electrodeposition of Pd. During Pd introduction, the presence of sulfuric acid in the electrolyte influences the shape of the Pd nanoparticles. Sulfate ions prevent the growth of the Pd, resulting in nanoparticles with sharp features. The fabricated Pd_PPy/PAN NFs are then incorporated as the active element in an electrochemical hydrogen peroxide (H2O2) biosensor. Tailoring the morphology of the Pd nanoparticles enables a minimum detectable limit of 1 × 10−9m H2O2, which is sufficiently low for monitoring diseases related to H2O2 concentration, such as Parkinson's disease and Alzheimer's disease. The low detection limit is achieved by coalescing detection of Pd and PPy.

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Palladium on Carbon-Catalyzed Silane-Reduction of Tertiary Carboxamides: Soluble Palladium Colloids are an Active Catalyst Species

Cited by 9 publications

References 79 publications

Continuous Ligand-Free Catalysis Using a Hybrid Polymer Network Support

Continuous Ligand-Free Catalysis Using a Hybrid Polymer Network Support

Catalytic Silane‐Reduction of Carboxylic Esters and Lactones: Selective Synthetic Methods to Aldehydes, Lactols, and Ethers via Silyl Acetal Intermediates

Fabrication of Shape‐Controlled Palladium Nanoparticle‐Decorated Electrospun Polypyrrole/Polyacrylonitrile Nanofibers for Hydrogen Peroxide Coalescing Detection

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