Search results for " elimination"
showing 10 items of 78 documents
Complexes of (CH3)2AuIII: synthesis, PMR and IR spectra
1975
Abstract The syntheses and reactivity of dimethylgold(III) complexes with multidentate ligands as TRIPHOS (i.e., 1,1,1-tris(diphenylphosphinomethyl)ethane) and TREN (i.e. 2,2′,2″-triaminotriethylamine) have been examined. I.r. spectra for the compounds in the solid state, conductivity and PMR data for solutions, lead to the assignment of an ionic formula [CH 3 ) 2 Au TRIPHOS] + [(CH 3 ) 2 AuCl 2 ] − where the gold(III) atoms are presumably four-coordinate. The complex (CH 3 ) 2 AuCl TREN in DMSO solution undergoes a reductive elimination reaction, as found for analogous dimethylgold(III) derivatives.
Multiple Roles of Isocyanides in Palladium-Catalyzed Imidoylative Couplings: A Mechanistic Study
2016
International audience; Kinetic, spectroscopic and computational studies examining a palladium-catalyzed imidoylative coupling highlight the dual role of isocyanides as both substrates and ligands for this class of transformations. The synthesis of secondary amides from aryl halides and water is presented as a case study. The kinetics of the oxidative addition of ArI with RNC-ligated Pd-0 species have been studied and the resulting imidoyl complex [(ArC=NR)Pd(CNR)(2)I] (Ar=4-F-C6H4, R = tBu) has been isolated and characterized by X-ray diffraction. The unprecedented ability of this RNC-ligated imidoyl-Pd complex to undergo reductive elimination at room temperature to give the amide in the p…
Diastereoselective Synthesis of Dialkylated Bis(phosphino)ferrocenes: Their Use in Promoting Silver-Mediated Nucleophilic Fluorination of Chloroquino…
2017
International audience; The diastereoselective synthesis of dialkylated ferrocenyl bis(phosphane)s bearing aryl, alkyl, and hetero- or polycyclic substituents on the phosphino groups is reported, together with their characterization in the solid state by X-ray structure analysis and in solution by multinuclear NMR spectroscopy. Introduction of various alkyl groups on the ferrocene backbone, namely, tert-butyl, isopropyl, and trimethylsilyl, has a significant influence on the stereoselectivity of the ensuing lithiation/phosphination reactions. Only the introduction of the tert-butyl groups ensures both a high yield and perfect diastereoselectivity, which leads to the exclusive formation of t…
Efficient CNF Encoding of Boolean Cardinality Constraints
2003
In this paper, we address the encoding into CNF clauses of Boolean cardinality constraints that arise in many practical applications. The proposed encoding is efficient with respect to unit propagation, which is implemented in almost all complete CNF satisfiability solvers. We prove the practical efficiency of this encoding on some problems arising in discrete tomography that involve many cardinality constraints. This encoding is also used together with a trivial variable elimination in order to re-encode parity learning benchmarks so that a simple Davis and Putnam procedure can solve them.
Xenobiotic Metabolism
1999
Publisher Summary This chapter reveals that one's body takes up significant amounts of material that are used neither as energy substrates nor as building blocks for biological matrices. Uptake of such xenobiotica occurs mainly with the food but also by inhalation or transdermally. If these compounds accumulated in the organism, the resulting body burden would have been enormous. Thus, efficient mechanisms for the excretion of such compounds that have their roots very early in the evolution of life have developed. The two major elimination pathways in humans are excretion via bile and excretion via urine. For volatile compounds, exhalation can represent the dominant mechanism of excretion. …
Hardware-efficient matrix inversion algorithm for complex adaptive systems
2012
This work shows an FPGA implementation for the matrix inversion algebra operation. Usually, large matrix dimension is required for real-time signal processing applications, especially in case of complex adaptive systems. A hardware efficient matrix inversion procedure is described using QR decomposition of the original matrix and modified Gram-Schmidt method. This works attempts a direct VHDL description using few predefined packages and fixed point arithmetic for better optimization. New proposals for intermediate calculations are described, leading to efficient logic occupation together with better performance and accuracy in the vector space algebra. Results show that, for a relatively s…
AuX3-Mediated Selective Head-to-Head Dimerization of Difluoropropargyl Amides
2009
A dimerization of difluoropropargyl amides by reaction with gold(III) halides is described. A reductive elimination of a divinylgold species can be invoked to rationalize its formation. Initial studies of the unusual reactivity of these 1,4-dihalo-1,3-dienes have been performed.
In vitro evaluation of poloxamer in situ forming gels for bedaquiline fumarate salt and pharmacokinetics following intramuscular injection in rats
2019
Graphical abstract
Organocatalytic Enantioselective Friedel–Crafts Aminoalkylation of Indoles in the Carbocyclic Ring
2016
The first general catalytic method for the, so far elusive, enantioselective Friedel−Crafts functionalization of indoles in the carbocyclic ring is presented. This transformation contrasts with the usual tendency of these heterocycles to react at the azole ring. For this purpose, the four regioisomeric hydroxy carbocyclic-substituted indoles were reacted with several isatinderived ketimines, using a Cinchona alkaloid-based squaramide, in a low 0.5−5 mol % catalyst loading, as a bifunctional catalyst. This methodology allows the functionalization of indoles in every position of the carbocyclic ring in a regio- and enantioselective fashion, by switching only the position of the hydroxy group …
Etherification of Functionalized Phenols with Chloroheteroarenes at Low Palladium Loading: Theoretical Assessment of the Role of Triphosphane Ligands…
2011
The present study highlights the potential of robust tridentate ferrocenylphosphanes with controlled conformation as catalytic auxiliaries in CO bond formation reactions. Air-stable palladium triphosphane systems are efficient for selective heteroaryl ether synthesis by using as little as 0.2 mol% of catalyst. These findings represent an economically attractive and clean etherification of functionalized phenols, electron-rich, electron-poor and para-, meta- or ortho-substituted substrates, with heteroaryl chlorides, including pyridines, hydroxylated pyridine, pyrimidines and thiazole. The etherification tolerates very important functions in various positions, such as cyano, methoxy, amino, …