Search results for "Agent"
showing 10 items of 8904 documents
Direct Difluorination–Hydroxylation, Trifluorination, and C(sp2)–H Fluorination of Enamides
2018
A direct double functionalization involving both difluorination and hydroxylation of enamides is reported. With the appropriate combination of an electrophilic fluorinating reagent and H2O, the most convenient and ecofriendly hydroxylating agent, the preparation of 3-(difluoroalkyl)-3-hydroxyisoindolin-1-ones was achieved under basic or Bronsted acidic conditions. Suitable conditions for trifluorination as well as C(sp2)–H fluorination were also identified. Subsequent asymmetric functionalization of the obtained gem-difluorinated products has also been demonstrated.
Light Induced C-C Coupling of 2-Chlorobenzazoles with Carbamates, Alcohols, and Ethers.
2016
A light induced, transition-metal-free C-C coupling reaction of 2-chlorobenzazoles with aliphatic carbamates, alcohols, and ethers is presented. Inexpensive reagents, namely sodium acetate, benzophenone, water, and acetonitrile, are employed in a simple reaction protocol using a cheap and widely available 25 W energy saving UV-A lamp at ambient temperature.
Metal- and Reagent-Free Anodic C−C Cross-Coupling of Phenols with Benzofurans leading to a Furan Metathesis
2018
Heterobiaryls consisting of a phenol and a benzofuran motif are of significant importance for pharmaceutical applications. An attractive sustainable, metal- and reagent-free, electrosynthetic, and highly efficient method, that allows access to (2-hydroxyphenyl)benzofurans is presented. Upon the electrochemical dehydrogenative C-C cross-coupling reaction, a metathesis of the benzo moiety at the benzofuran occurs. This gives rise to a substitution pattern at the hydroxyphenyl moiety which would not be compatible by a direct coupling process. The single-step protocol is easy to conduct in an undivided electrolysis cell, therefore scalable, and inherently safe.
N-Acyl-glutarimides: Effect of Glutarimide Ring on the Structures of Fully Perpendicular Twisted Amides and N–C Bond Cross-Coupling
2020
N-Acyl-glutarimides have emerged as the most reactive precursors for N-C(O) bond cross-coupling reactions to date, wherein the reactivity is driven by ground-state destabilization of the amide bond. Herein, we report a full study on the effect of a glutarimide ring on the structures, electronic properties, and reactivity of fully perpendicular N-acyl-glutarimide amides. Most notably, this report demonstrates the generality of deploying N-acyl-glutarimides to achieve full twist of the acyclic amide bond, and results in the discovery of N-acyl-glutarimide amide with an almost perfect twist value, τ = 89.1°. X-ray structures of five new N-acyl-glutarimides are reported. Reactivity studies in t…
N-Cobaltocenium Amide as Reactive Nucleophilic Reagent for Donor–Acceptor Bimetallocenes
2017
Deprotonation of the aminocobaltocenium ion [Cc-NH2]+ ([H-1]+) generates the nucleophilic imine CcNH (1). Reaction of 1 with acid chlorides R–COCl (R = Ph, Fc, and Cc+) yields the reference amide [Ph-CO-NH-Cc]+ (2+) and the amide-linked hetero- and homobimetallocenes [Fc-CO-NH-Cc]+ (3+) and [Cc-CO-NH-Cc]2+ (42+), respectively. Cation–anion interactions of charged amides 2+–42+ in the solid state and in solution are probed by single crystal X-ray diffraction and NMR and IR spectroscopy. Intramolecular metal–metal interactions in donor–acceptor heterobimetallocene 3+ and in mixed-valent homobimetallocene 4+ (prepared electrochemically) are discussed within the Marcus–Hush framework aided by s…
Electrochemical Arylation Reaction
2018
Arylated products are found in various fields of chemistry and represent essential entities for many applications. Therefore, the formation of this structural feature represents a central issue of contemporary organic synthesis. By the action of electricity the necessity of leaving groups, metal catalysts, stoichiometric oxidizers, or reducing agents can be omitted in part or even completely. The replacement of conventional reagents by sustainable electricity not only will be environmentally benign but also allows significant short cuts in electrochemical synthesis. In addition, this methodology can be considered as inherently safe. The current survey is organized in cathodic and anodic con…
Amino‐Substituted Ferra‐bis(tricarbollides) − Metallatricarbaboranes Designed for Linear Molecular Constructions
2004
Reactions between high purity FeCl2 and the anion [nido-7-(tBuHN)-7,8,9-C3B8H10)]− (1−) have been used for efficient syntheses of the twelve-vertex double-cluster metallatricarbollide complexes of the para,para (p,p) type [closo-9,9′(RHN)2-commo-2,2′-FeII-1,7,9-(C3B8H10)-1′,7′,9′-(C3B8H10)] (2) (2a, R = tBu and 2b, R = H) (yields 42−45% for 2a). Compound 2b, which contains two reactive amino substituents conveniently attached to the tricarbollide subclusters in p-positions with respect to the metal center, was prepared via facile cleavage of the tBu substituent in 2a either by AlCl3 or by thermal means. The structure of 2b constitutes a good setting for the synthesis of building blocks for …
Carbon monoxide activation by a molecular aluminium imide: C-O bond cleavage and C-C bond formation
2020
Anionic molecular imide complexes of aluminium are accessible via a rational synthetic approach involving the reactions of organo azides with a potassium aluminyl reagent. In the case of K2 [(NON)Al(NDipp)]2 (NON=4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethyl-xanthene; Dipp=2,6-diisopropylphenyl) structural characterization by X-ray crystallography reveals a short Al-N distance, which is thought primarily to be due to the low coordinate nature of the nitrogen centre. The Al-N unit is highly polar, and capable of the activation of relatively inert chemical bonds, such as those found in dihydrogen and carbon monoxide. In the case of CO, uptake of two molecules of the substrate…
Edge-Based Missing Data Imputation in Large-Scale Environments
2021
Smart cities leverage large amounts of data acquired in the urban environment in the context of decision support tools. These tools enable monitoring the environment to improve the quality of services offered to citizens. The increasing diffusion of personal Internet of things devices capable of sensing the physical environment allows for low-cost solutions to acquire a large amount of information within the urban environment. On the one hand, the use of mobile and intermittent sensors implies new scenarios of large-scale data analysis
Targeted delivery of hydrogen for the bioremediation of aquifers contaminated by dissolved chlorinated compounds.
2019
Dihydrogen (H2) gas injection is a promising option to enhance the reductive biodehalogenation of contaminants in groundwater. However, it is challenging to ensure its targeted delivery at the right places in plumes, and for the long times required for bioremediation. In this paper, the ability of surfactant foam to retain H2 in the saturated zone and to enhance its release in the dissolved form was compared to traditional biosparging. H2 gas was injected, either alone, or as foam, in a 2D saturated cell packed with glass beads. This cell was continuously flushed with deoxygenated water to mimic aquifer circulation, and H2 was studied both in terms of gas distribution in the cell and dissol…