69 research outputs found
Catalytic direct amidations in tert-butyl acetate using B(OCH2CF3)3
Catalytic direct amidation reactions have been the focus of considerable recent research effort, due to the widespread use of amide formation processes in pharmaceutical synthesis. However, the vast majority of catalytic amidations are performed in non-polar solvents (aromatic hydrocarbons, ethers) which are typically undesirable from a sustainability perspective, and are often poor at solubilising polar carboxylic acid and amine substrates. As a consequence, most catalytic amidation protocols are unsuccessful when applied to polar and/or functionalised substrates of the kind commonly used in medicinal chemistry. In this paper we report a practical and useful catalytic direct amidation reaction using tert-butyl acetate as the reaction solvent. The use of an ester solvent offers improvements in terms of safety and sustainability, but also leads to an improved reaction scope with regard to polar substrates and less nucleophilic anilines, both of which are important components of amides used in medicinal chemistry. An amidation reaction was scaled up to 100 mmol and proceeded with excellent yield and efficiency, with a measured process mass intensity of 8
Dihalohydration of Alkynols: A Versatile Approach to Diverse Halogenated Molecules
In this paper we outline how dihalohydration reactions of propargylic alcohols can be used to access a wide variety of useful halogenated building blocks. A novel procedure for dibromohydration of alkynes has been developed, and a selection of dichloro and dibromo diols and cyclic ethers were synthesized. The dihalohydration of homo‐propargylic alcohols provides a useful route to 3‐halofurans, which were shown to readily undergo cycloaddition reactions under mild conditions. Finally, a novel ring‐expansion of propargylic alcohols containing a cyclopropylalkyne provides access to halogenated alkenylcyclobutanes
The SuperCam Instrument Suite on the Mars 2020 Rover: Science Objectives and Mast-Unit Description
On the NASA 2020 rover mission to Jezero crater, the remote determination of the texture, mineralogy and chemistry of rocks is essential to quickly and thoroughly characterize an area and to optimize the selection of samples for return to Earth. As part of the Perseverance payload, SuperCam is a suite of five techniques that provide critical and complementary observations via Laser-Induced Breakdown Spectroscopy (LIBS), Time-Resolved Raman and Luminescence (TRR/L), visible and near-infrared spectroscopy (VISIR), high-resolution color imaging (RMI), and acoustic recording (MIC). SuperCam operates at remote distances, primarily 2-7 m, while providing data at sub-mm to mm scales. We report on SuperCam's science objectives in the context of the Mars 2020 mission goals and ways the different techniques can address these questions. The instrument is made up of three separate subsystems: the Mast Unit is designed and built in France; the Body Unit is provided by the United States; the calibration target holder is contributed by Spain, and the targets themselves by the entire science team. This publication focuses on the design, development, and tests of the Mast Unit; companion papers describe the other units. The goal of this work is to provide an understanding of the technical choices made, the constraints that were imposed, and ultimately the validated performance of the flight model as it leaves Earth, and it will serve as the foundation for Mars operations and future processing of the data.In France was provided by the Centre National d'Etudes Spatiales (CNES). Human resources were provided in part by the Centre National de la Recherche Scientifique (CNRS) and universities. Funding was provided in the US by NASA's Mars Exploration Program. Some funding of data analyses at Los Alamos National Laboratory (LANL) was provided by laboratory-directed research and development funds
Gold-Catalyzed Hydrophenoxylation of Propargylic Alcohols and Amines: Synthesis of Phenyl Enol Ethers
A practical method for the synthesis of phenyl enol ethers is reported. The combination of a gold(I) catalyst and potassium carbonate selectively mediates the addition of phenols to propargylic alcohols/amines in a chemo-, regio-, and stereoselective fashion in high yield. The resulting enol ethers are formed exclusively with a Z-configuration and can be obtained from a wide array of phenols and propargylic alcohols or amines with the reaction showing excellent functional group tolerance
Recommended from our members
Protein Conjugation by Electrophilic Alkynylation Using 5-(Alkynyl)dibenzothiophenium Triflates.
5-(Alkynyl)dibenzothiophenium triflates are introduced as new reagents to prepare different protein conjugates through site-selective cysteine alkynylation. The protocol developed allows a highly efficient label of free cysteine-containing proteins with relevant biological roles, such as ubiquitin, the C2A domain of Synaptotagmin-I, or HER2 targeting nanobodies. An electrophilic bis-alkynylating reagent was also designed. The second alkynylating handle thus introduced in the desired protein enables access to protein-thiol, protein-peptide, and protein-protein conjugates, and even diubiquitin dimers can be prepared through this approach. The low excess of reagent needed, mild reaction conditions used, short reaction times, and stability of the S-C(alkyne) bonds at physiological conditions make this approach an interesting addition to the toolbox of classical, site-selective cysteine-conjugation methods
Poly-(styrene sulphonic acid): An acid catalyst from polystyrene waste for reactions of interest in biomass valorization
This article reports on the use of poly-(styrene sulphonic acid) (PSSA) prepared by sulphonation of polystryrene waste as catalyst in reactions demanding acid sites. Two different waste derived catalysts (waste to catalyst, WTC) were studied: soluble PSSA (WTC-PSSA) and solid SiO2-PSSA nanocomposite (WTC-SiO2-PSSA). The catalytic properties of these waste derived acid catalysts have been explored in three different reactions of interest in biomass valorization: biodiesel synthesis, xylose dehydration to furfural and furfural oxidation to maleic and succinic acids. The results show that both soluble and nanocomposite WTC catalysts present promising catalytic properties. The WTC-PSSA requires ultrafiltration for reutilization whereas the WTC-SiO2-PSSA can be separated from the reaction mixtures by more usual techniques (centrifugation or conventional filtration). Further research is required for improving the hydrothermal stability of WTC-SiO2-PSSA in order to substantially reduce the leaching of polymer that takes place during the catalytic runs.This work was funded by the Spanish Ministry of Economy and Competitiveness (Project CTQ2012-38204-C03-01, CARBIOCAT) and the Autonomous Government of Madrid (S2009/ENE-1660, CARDENER-CM partly funded by FSE funds).Peer Reviewe
A stochastic model of the process of sequence casting of steel, taking into account imperfect mixing
The process of sequential casting of steel, i.e. the procedure that implies a continuous change in the composition of the steel in the casting process of different steel grades, can be easily modelled assuming a perfect and instantaneous mix of the materials in the tundish. However, experimental evidence based on the measure of the local composition of steel billets obtained through this process suggests that the mixing of different steel grades in the tundish cannot be considered either perfect or instantaneous. An improved stochastic model, taking into account these effects, is presented and validated against the experimental results obtained using the laser-induced breakdown spectroscopy technique, assisted by an artificial neural network. In spite of the simplicity of the model proposed, the agreement between its predictions and the experimental results is remarkable
Eco-friendly nanocomposite products based on BPA-free epoxy–silica hybrid materials for stone conservation
- …