Cu(OAc)2-Promoted Ortho C(sp2)–H Amidation of 8-Aminoquinoline Benzamide with Acyl Azide: Selective Formation of Aroyl or Acetyl Amide Based on Catalyst Loading

2018 ◽  
Vol 83 (19) ◽  
pp. 11758-11767 ◽  
Author(s):  
Tubai Ghosh ◽  
Pintu Maity ◽  
Brindaban C. Ranu
Keyword(s):  
Catalyst Loading ◽  
Acyl Azide ◽  
Selective Formation

Metal-Metal Cooperative Bond Activation by Heterobimetallic Alkyl, Aryl, and Acetylide PtII/CuI Complexes

2020 ◽  
Author(s):  
Shubham Deolka ◽  
Orestes Rivada Wheelaghan ◽  
Sandra Aristizábal ◽  
Robert Fayzullin ◽  
Shrinwantu Pal ◽  
...  
Keyword(s):  
Alkyl Group ◽  
Bond Activation ◽  
Bond Cleavage ◽  
Terminal Alkyne ◽  
Alkyl Aryl ◽  
Metal Metal ◽  
The Stability ◽  
Selective Formation ◽  
Organoplatinum Compounds

We report selective formation of heterobimetallic PtII/CuI complexes that demonstrate how facile bond activation processes can be achieved by altering reactivity of common organoplatinum compounds through their interaction with another metal center. The interaction of the Cu center with Pt center and with a Pt-bound alkyl group increases the stability of PtMe2 towards undesired rollover cyclometalation. The presence of the CuI center also enables facile transmetalation from electron-deficient tetraarylborate [B(ArF)4]- anion and mild C-H bond cleavage of a terminal alkyne, which was not observed in the absence of an electrophilic Cu center. The DFT study indicates that the role of Cu center acts as a binding site for alkyne substrate, while activating its terminal C-H bond.

Gold Catalyzed Hydroamination of Propargylic Alcohols: Controlling Divergent Reaction Pathways to Access 1,3-Aminoalcohols, 3-Hydroxyketones or 3-Aminoketones

2018 ◽  
Author(s):  
Victor Laserna ◽  
Tom Sheppard
Keyword(s):  
Gold Catalysis ◽  
Reaction Pathways ◽  
High Yield ◽  
Reaction Conditions ◽  
Propargylic Alcohols ◽  
Catalytic Quantity ◽  
Selective Formation ◽  
General Method

A versatile approach to the valorization of propargylic alcohols is reported, enabling controlled access to three different products from the same starting materials. Firstly, a general method for the hydroamination of propargylic alcohols with anilines is described using gold catalysis to give 3-hydroxy imines with complete regioselectivity. These 3-hydroxyimines can be reduced to give 1,3-aminoalcohols with high syn seletivity. Alternatively, by using a catalytic quantity of aniline, 3-hydroxyketones can be obtained in high yield directly from propargylic alcohols. Further manipulation of the reaction conditions enables the selective formation of 3-aminoketones via a rearrangement/hydroamination pathway.<br>

Hafnium(IV) Chloride Catalyzes Highly Efficient Acetalization of Carbonyl Compounds

2019 ◽  
Vol 16 (6) ◽  
pp. 913-920 ◽  
Author(s):  
Israel Bonilla-Landa ◽  
Emizael López-Hernández ◽  
Felipe Barrera-Méndez ◽  
Nadia C. Salas ◽  
José L. Olivares-Romero
Keyword(s):  
Microwave Heating ◽  
Reaction Times ◽  
Protecting Groups ◽  
Catalyst Loading ◽  
Selective Protection ◽  
Highly Efficient ◽  
Aldehydes And Ketones ◽  
High Yields ◽  
Novel Catalyst ◽  
Acid Labile

Background: Hafnium(IV) tetrachloride efficiently catalyzes the protection of a variety of aldehydes and ketones, including benzophenone, acetophenone, and cyclohexanone, to the corresponding dimethyl acetals and 1,3-dioxolanes, under microwave heating. Substrates possessing acid-labile protecting groups (TBDPS and Boc) chemoselectively generated the corresponding acetal/ketal in excellent yields. Aim and Objective: In this study. the selective protection of aldehydes and ketones using a Hafnium(IV) chloride, which is a novel catalyst, under microwave heating was observed. Hence, it is imperative to find suitable conditions to promote the protection reaction in high yields and short reaction times. This study was undertaken not only to find a novel catalyst but also to perform the reaction with substrates bearing acid-labile protecting groups, and study the more challenging ketones as benzophenone. Materials and Methods: Using a microwave synthesis reactor Monowave 400 of Anton Paar, the protection reaction was performed on a raging temperature of 100°C ±1, a pressure of 2.9 bar, and an electric power of 50 W. More than 40 substrates have been screened and protected, not only the aldehydes were protected in high yields but also the more challenging ketones such as benzophenone were protected. All the products were purified by simple flash column chromatography, using silica gel and hexanes/ethyl acetate (90:10) as eluents. Finally, the protected substrates were characterized by NMR 1H, 13C and APCI-HRMS-QTOF. Results: Preliminary screening allowed us to find that 5 mol % of the catalyst is enough to furnish the protected aldehyde or ketone in up to 99% yield. Also it was found that substrates with a variety of substitutions on the aromatic ring (aldehyde or ketone), that include electron-withdrawing and electrondonating group, can be protected using this methodology in high yields. The more challenging cyclic ketones were also protected in up to 86% yield. It was found that trimethyl orthoformate is a very good additive to obtain the protected acetophenone. Finally, the protection of aldehydes with sensitive functional groups was performed. Indeed, it was found that substrates bearing acid labile groups such as Boc and TBDPS, chemoselectively generated the corresponding acetal/ketal compound while keeping the protective groups intact in up to 73% yield. Conclusion: Hafnium(IV) chloride as a catalyst provides a simple, highly efficient, and general chemoselective methodology for the protection of a variety of structurally diverse aldehydes and ketones. The major advantages offered by this method are: high yields, low catalyst loading, air-stability, and non-toxicity.

Catalytic Neutralization of Naphthenic Acid from Petroleum Crude Oil by Using Cerium Oxide Catalyst and 2- Methylimidazole in Polyethylene Glycol

2020 ◽  
Vol 13 ◽  
Author(s):  
Norshahidatul Akmar Mohd Shohaimi ◽  
Norfakhriah Jelani ◽  
Ahmad Zamani Ab Halim ◽  
Nor Hakimin Abdullah ◽  
Nurasmat Mohd Shukri
Keyword(s):  
Polyethylene Glycol ◽  
Crude Oil ◽  
Cerium Oxide ◽  
Active Sites ◽  
Naphthenic Acid ◽  
Naphthenic Acids ◽  
Catalyst Loading ◽  
High Concentration ◽  
Oil Refineries ◽  
Al2o3 Catalyst

: The presence of relatively high naphthenic acid in crude oil may contribute to the major corrosion in oil pipelines and distillation units in crude oil refineries. Thus, high concentration Naphthenic Acids crude oil is considered tobe of low quality and is marketed at lower prices. In order to overcome this problem, neutralization method had been developed to reduce the TAN value in crude oil. In this study, crude oil from Petronas Penapisan Melaka was investigated. The parameters studied were reagent concentration, catalyst loading, calcination temperature and reusability of the potential catalyst. Basic chemical used were 2- methylimidazole in polyethylene glycol (PEG 600) with concentration 100, 500 and 1000 ppm. Cerium oxide-based catalysts supported onto alumina prepared with different calcination temperatures. The catalyst was characterized by using Brunauer-Emmett-Teller (BET), Fourier Transform Infrared Spectroscopy (FTIR) and Thermogravimetry Analysis-Differential Thermal Gravity (TGA-DTG) to study physical properties of the catalyst. The Ce/Al2O3 catalyst calcined at 1000°C was the best catalyst due to larger surface area formation which lead to increment of active sites thus will boost the catalytic activity. The result showed that the Ce/Al2O3 catalyst meet Petronas requirement as the TAN value reduced to 0.6 mgKOH/g from original TAN value of 4.22 mgKOH/g. The best reduction of TAN was achieved by using catalyst loading of 0.39% and reagent of 1000 ppm.

Analysis of NiMoP/γ-Al2O3 Catalyst Preparation with Impregnation and Microwave Polyol Methods for Bio-Jet Production

2020 ◽  
Vol 1000 ◽  
pp. 257-264
Author(s):  
Bambang Heru Susanto ◽  
Joshua Raymond Valentino Siallagan
Keyword(s):  
Coconut Oil ◽  
Catalyst Preparation ◽  
Operating Conditions ◽  
Catalyst Loading ◽  
Impregnation Method ◽  
Conversion Yield ◽  
Jet Production ◽  
Cracking Process ◽  
Catalyst Impregnation ◽  
Rate Conversion

Bio-Jet could be produced by the synthesis of vegetable oil through the hydrodeoxygenation, decarboxylation, decarbonization, and catalytic cracking process. Physical characteristics, activities, and selectivity of the catalyst used will determine the rate, conversion, and yield of the reaction that being carried out. This study aims to compare and obtain the best characteristics of NiMoP/γ-Al2O3 catalysts synthesized using two types of preparation, impregnation and microwave polyol methods, which will be used for bio-jet production. The impregnation method takes more than 24 hours for catalyst preparation, while microwave polyols that use microwaves can synthesize catalysts faster. Both catalysts have almost the same loading on the weight of the catalyst, which in the microwave polyol method has a more dispersed promotor and active site, although the crystallinity level is deficient and tends to be amorphous compared to the impregnation method with high crystallinity. In bio-jet synthesis reaction with operating conditions of 5% catalyst loading by comparison to Coconut Oil, 400°C, and 15 bar, the conversion, yield, and selectivity of catalyst impregnation were 91.705%, 47.639%, and 84.511%, while microwave polyol catalysts were 90.296%, 42.752%, and 82.517%, respectively. In conclusion, microwave polyol provides a more effective and efficient preparation method.

scholarly journals Investigation of Gas Diffusion Electrode Systems for the Electrochemical CO2 Conversion

Catalysts ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 482
Author(s):  
Hilmar Guzmán ◽  
Federica Zammillo ◽  
Daniela Roldán ◽  
Camilla Galletti ◽  
Nunzio Russo ◽  
...  
Keyword(s):  
Carbon Capture ◽  
Active Sites ◽  
Co2 Reduction ◽  
Gas Diffusion ◽  
Gas Diffusion Electrode ◽  
Catalyst Loading ◽  
Co2 Conversion ◽  
Atmospheric Conditions ◽  
Electrochemical Co2 Reduction ◽  
Liquid Products

Electrochemical CO2 reduction is a promising carbon capture and utilisation technology. Herein, a continuous flow gas diffusion electrode (GDE)-cell configuration has been studied to convert CO2 via electrochemical reduction under atmospheric conditions. To this purpose, Cu-based electrocatalysts immobilised on a porous and conductive GDE have been tested. Many system variables have been evaluated to find the most promising conditions able to lead to increased production of CO2 reduction liquid products, specifically: applied potentials, catalyst loading, Nafion content, KHCO3 electrolyte concentration, and the presence of metal oxides, like ZnO or/and Al2O3. In particular, the CO productivity increased at the lowest Nafion content of 15%, leading to syngas with an H2/CO ratio of ~1. Meanwhile, at the highest Nafion content (45%), C2+ products formation has been increased, and the CO selectivity has been decreased by 80%. The reported results revealed that the liquid crossover through the GDE highly impacts CO2 diffusion to the catalyst active sites, thus reducing the CO2 conversion efficiency. Through mathematical modelling, it has been confirmed that the increase of the local pH, coupled to the electrode-wetting, promotes the formation of bicarbonate species that deactivate the catalysts surface, hindering the mechanisms for the C2+ liquid products generation. These results want to shine the spotlight on kinetics and transport limitations, shifting the focus from catalytic activity of materials to other involved factors.

Y(OTf)3-catalyzed Phosphorylation of 2H-Chromene Hemiacetals with P(O)-H compounds to 2-Phosphorylated 2H-Chromenes

2021 ◽  
Author(s):  
Long Chen ◽  
Shi-Lu Zheng ◽  
Yun-Xiang Zou ◽  
Zhong Wen ◽  
Jiafu Lin ◽  
...  
Keyword(s):  
Catalyst Loading ◽  
Facile Synthesis ◽  
Reaction Conditions ◽  
Low Catalyst Loading

Facile synthesis of 2-phosphorylated 2H-chromenes has been accomplished herein via a Y(OTf)3-catalyzed dehydrative coupling of 2H-chromene hemiacetals with P(O)-H compounds. This protocol features low catalyst loading, mild reaction conditions, broad...

Hydrosilylation and Mukaiyama Aldol-type Reactions of Imine and Quinoline Derivatives Catalyzed by a Mesoionic Carbene-Stabilized Borenium Ion

2021 ◽  
Author(s):  
Joshua J. Clarke ◽  
Karthik Devaraj ◽  
Brian Bestvater ◽  
Ryoto Kojima ◽  
Patrick Eisenberger ◽  
...  
Keyword(s):  
Room Temperature ◽  
Secondary Amines ◽  
Catalyst Loading ◽  
Quinoline Derivatives ◽  
Mukaiyama Aldol

Aldimines and ketimines containing electron-donating and electron-withdrawing groups can be hydrosilylated with borenium catalysts at as low as 1 mol% catalyst loading at room temperature, providing the corresponding secondary amines...

Selective Formation of a Supramolecular Coordination Complex in the Nanometre Scale with a Ferrocene-based Phospholane Ligand

2021 ◽  
Author(s):  
Reinhard Hoy ◽  
Toni Grell ◽  
Peter Lönnecke ◽  
Evamarie Hey-Hawkins
Keyword(s):  
Coordination Complex ◽  
Supramolecular Coordination ◽  
Selective Formation

A straightforward synthesis of the tetradentate phospholane ligand 1 is reported. The 2:1 [M:L] reaction of 1 with [AuCl(tht)] (tht = tetrahydrothiophen) resulted in a 4:2 [M:L] supramolecular coordination complex...

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