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Subsequent Transformations (subsequent + transformation)
Selected AbstractsBase-Catalysed Intramolecular Hydroamination of Vinyl Sulfides,EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 11 2009Coralie Quinet Abstract Small amounts of n -butyllithium catalyse the highly efficient hydroamination of a large variety of vinyl sulfides. This novel methodology offers an easy access to a wide range of nitrogen heterocycles, including simple pyrrolidines and piperidines, as well as more complex bicyclic compounds. Subsequent transformations of the sulfur group led to the formation of functionalised alkaloid-like substructures.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Synthesis of an Inherently Chiral Calix[4]arene Amino Acid and Its Derivatives: Their Application to Asymmetric Reactions as OrganocatalystsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 12 2009Seiji Shirakawa Abstract The synthesis of an inherently chiral calix[4]arene amino acid as a chiral building block has been achieved in order for subsequent transformation to various types of inherently chiral calix[4]arenes. The optically pure, inherently chiral calix[4]arene amino acids were prepared by the separation of a diastereomeric mixture of calix[4]arene amino acid derivatives bearing a (R)-BINOL moiety. The separated optically pure calix[4]arene amino acid derivatives with a (R)-BINOL moiety were easily transformed to novel inherently chiral calix[4]arenes containing an amino alcohol structure or a quaternary ammonium moiety. These optically pure chiral calix[4]arenes were applied to asymmetric reactions as organocatalysts.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Microbial communities in roots of Pinus sylvestris seedlings with damping-off symptoms in two forest nurseries as determined by ITS1/2 rDNA sequencingFOREST PATHOLOGY, Issue 4 2009H. Kwa Summary A methodological molecular procedure, which included extraction and cloning of the ITS1/2 rDNA of root-associated organisms with subsequent transformation and sequencing of representative clones, was effective for detection, discrimination and determination of the frequency of the main damping-off pathogens in roots of Pinus sylvestris seedlings growing in different forest-tree nursery soils and exhibiting different rates of disease progress. Roots exhibiting slower damping-off progression were colonized by Fusarium oxysporum, Neonectria radicicola (Ascomycota) and Pythium spp. (Oomycota), which comprised 50% of the microbial community. Roots exhibiting faster damping-off progression were dominated by Thanatephorus cucumeris (Basidiomycota), which comprised 80% of the microbial community. The microbial community was more diverse in roots with slower damping-off progression (14 species) than in roots with faster disease progression (seven species). [source] Large-Scale Synthesis of Long Crystalline Cu2-xSe Nanowire Bundles by Water-Evaporation-Induced Self-Assembly and Their Application in Gas SensingADVANCED FUNCTIONAL MATERIALS, Issue 11 2009Jun Xu Abstract By a facile water evaporation process without adding any directing agent, Cu2-xSe nanowire bundles with diameters of 100,300,nm and lengths up to hundreds of micrometers, which comprise crystalline nanowires with diameters of 5,8,nm, are obtained. Experiments reveal the initial formation/stacking of CuSe nanoplates and the subsequent transformation to the Cu2-xSe nanowire bundles. A water-evaporation-induced self-assembly (WEISA) mechanism is proposed, which highlights the driving force of evaporation in promoting the nanoplate stacking, CuSe-to-Cu2-xSe transformation and the growth/bundling of the Cu2-xSe nanowires. The simplicity, benignancy, scalability, and high-yield of the synthesis of this important nanowire material herald its numerous applications. As one example, the use of the Cu2-xSe nanowire bundles as a photoluminescence-type sensor of humidity is demonstrated, which shows good sensitivity, ideal linearity, quick response/recovery and long lifetime in a very wide humidity range at room temperature. [source] "Our Usable Past": A Historical Contextual Approach to Administrative ValuesPUBLIC ADMINISTRATION REVIEW, Issue 5 2009Donald P. Moynihan In responding to Professor Lynn's criticism that the field of public administration has been insufficiently attentive to law, this article offers an alternative perspective on the source of administrative legitimacy. Leonard White understood that public administration is shaped by its broader context. It does not assert its own values but, in an effort to maintain legitimacy, reflects the political and cultural values of its environment. In White's time, the extraordinary challenges that the state faced, and its subsequent transformation, demanded a management capacity that previously had not existed. While the role of law as a formal means of control is generally accepted, it must take its place with management and other administrative values in the exercise of legal discretionary behavior. Asserting law, or any other single administrative value, as dominant undercuts other values that act as sources of legitimacy. [source] Identification and characterization of a new conserved motif within the presequence of proteins targeted into complex diatom plastidsTHE PLANT JOURNAL, Issue 2 2005Oliver Kilian Summary Several groups of algae evolved by secondary endocytobiosis, which is defined as the uptake of a eukaryotic alga into a eukaryotic host cell and the subsequent transformation of the endosymbiont into an organelle. Due to this explicit evolutionary history such algae possess plastids that are surrounded by either three or four membranes. Protein targeting into plastids of these organisms depends on N-terminal bipartite presequences consisting of a signal and a transit peptide domain. This suggests that different protein targeting systems may have been combined during establishment of secondary endocytobiosis to enable the transport of proteins into the plastids. Here we demonstrate the presence of an apparently new type of transport into diatom plastids. We analyzed protein targeting into the plastids of diatoms and identified a conserved amino acid sequence motif within plastid preprotein targeting sequences. We expressed several diatom plastid presequence:GFP fusion proteins with or without modifications within that motif in the diatom Phaeodactylum tricornutum and found that a single conserved phenylalanine is crucial for protein transport into the diatom plastids in vivo, thus indicating the presence of a so far unknown new type of targeting signal. We also provide experimental data about the minimal requirements of a diatom plastid targeting presequence and demonstrate that the signal peptides of plastid preproteins and of endoplasmic reticulum-targeted preproteins in diatoms are functionally equivalent. Furthermore we show that treatment of the cells with Brefeldin A arrests protein transport into the diatom plastids suggesting that a vesicular transport step within the plastid membranes may occur. [source] Preparation of ,2 -Amino Acid Derivatives (,2hThr, ,2hTrp, ,2hMet, ,2hPro, ,2hLys, Pyrrolidine-3-carboxylic Acid) by Using DIOZ as Chiral Auxiliary,HELVETICA CHIMICA ACTA, Issue 8 2005Francois Gessier The title compounds were prepared from valine-derived N -acylated oxazolidin-2-ones, 1,3, 7, 9, by highly diastereoselective (,,90%) Mannich reaction (,,4,6; Scheme,1) or aldol addition (,,8 and 10; Scheme,2) of the corresponding Ti- or B-enolates as the key step. The superiority of the ,5,5-diphenyl-4-isopropyl-1,3-oxazolidin-2-one' (DIOZ) was demonstrated, once more, in these reactions and in subsequent transformations leading to various t -Bu-, Boc-, Fmoc-, and Cbz-protected ,2 -homoamino acid derivatives 11,23 (Schemes,3,6). The use of , -bromo-acyl-oxazolidinones 1,3 as starting materials turned out to open access to a variety of enantiomerically pure trifunctional and cyclic carboxylic-acid derivatives. [source] Kinetics and mechanism for the H-for-X exchange process in the H + C6H5X reactions: A computational studyINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 11 2001I. V. Tokmakov The addition of H atoms to benzene and toluene and subsequent transformations were investigated using high level ab initio and density functional theory methods. Molecular structures and vibrational frequencies calculated at the B3LYP/6-311++G(d,p) level of theory were used in combination with adjusted G2M energetic parameters for RRKM rate constant calculations. Standard heats of formation for cyclohexadienyl and cyclohexadienyl, 6-methyl radicals calculated through isodesmic reactions amounted to 49.5 ± 2 and 42.9 ± 3 kcal/mol, respectively. Rate constants for various elementary reactions involved in the H-for-X exchange (X = D, CH3) were calculated and closely correlated with the available experimental kinetic data. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 633,653, 2001 [source] The Fouling Behaviour of Sodium Aluminosilicate Polytypes in High Ionic Strength Caustic Media Heat ExchangersASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING, Issue 1-2 2006J. Addai-Mensah Sodium aluminosilicate (SAS) scale formation, simulating high ionic strength caustic media process heat exchanger fouling, has been investigated for a temperature range of 30,240°C. Findings from several studies performed with a variety of liquor, substrate-type and agitation conditions show that SAS polytypes; i.e. amorphous, zeolite A, sodalite and cancrinite phases, differing in thermodynamic stability and kinetic behaviour may deposit. The polytypes formed and subsequent transformations to more thermodynamically stable phases are strongly dependent on liquor composition, temperature and time. The scale deposition process is substrate- mediated heterogeneous nucleation and particle growth (precipitation foulin&, which may be accompanied by bulk liquor-nucleated solids adsorption (particulate fouling) at suficiently high supersaturations. Liquor seeding with stable SAS solid phases is found to be efective in mitigating fouling. The precipitation fouling behaviour is principally determined by the clystallo-chemical nature of the SAS polytype and the solution conditions. The substrate (mild steel, 316 stainless steel, nickel and tef2on) surface physico-chemical structure has a signlficant impact on the scale particle morphology and layer structure, particularly at high temperatures. [source] Synthesis of Enantiopure Sulfonimidamides and Elucidation of Their Absolute Configuration by Comparison of Measured and Calculated CD Spectra and X-Ray Crystal Structure DeterminationCHEMISTRY - A EUROPEAN JOURNAL, Issue 2 2010Christin Worch Abstract Straightforward syntheses of enantiopure N -benzoyl- and N - tert -butyloxycarbonyl-protected sulfonimidamides, which can be used as building blocks in newly designed catalysts, are presented. Key synthetic step is a dynamic resolution of a racemic sulfinic acid sodium salt. All subsequent transformations proceed stereospecifically. The absolute configurations at the sulfur atoms of both sulfonimidamides were determined by comparison of measured and calculated CD spectra. An X-ray crystal structure determination of a sulfonimidoylguanidine derivative confirmed this result. [source] Asymmetric Allylation of Methyl Ketones by Using Chiral Phenyl CarbinolsCHEMISTRY - A EUROPEAN JOURNAL, Issue 25 2009Abstract To methyl or to alkyl? High induced facial selectivities and excellent yields are obtained in the allylation of aliphatic methyl ketones by using a structurally simple phenylbenzyl auxiliary to give the corresponding homoallylic ethers (see scheme). The transferred auxiliary has a very good protecting quality and can easily be removed. Novel chiral auxiliaries for the stereoselective allylation of aliphatic methyl ketones with allyltrimethylsilane and their use in the synthesis of homoallylic ethers are described. In a multicomponent domino process catalyzed by trifluoromethanesulfonic acid, the allyl moiety and the auxiliary are transferred onto the substrate to yield tertiary homoallylic ethers. The most useful auxiliary for a general application turned out to be the trimethylsilyl ether of phenyl benzyl carbinol with an induced diastereoselectivity of 90:10 using ethyl methyl ketone and 94:6 using isopropyl methyl ketone as substrates. The transferred substituted benzyl moiety has good protecting properties in subsequent transformations and can easily be removed under reductive conditions to provide the corresponding homoallylic alcohol. The origin of the high selectivity could be elucidated by identifying the relevant transition states using quantum-chemical calculations. An excellent agreement between calculated and experimentally observed selectivities was obtained assuming an oxocarbenium ion as intermediate. [source] A New, Efficient and Stereoselective Synthesis of Tricyclic and Tetracyclic Compounds by Samarium Diiodide Induced Cyclisations of Naphthyl-Substituted Arylketones,An Easy Access to Steroid-Like SkeletonsCHEMISTRY - A EUROPEAN JOURNAL, Issue 21 2007Francesca Aulenta Dr. Abstract In this report, we present the application of samarium diiodide induced cyclisations of naphthyl-substituted ketones towards an easy and stereoselective access to tri- and tetracyclic-functionalised compounds. Typical naphthalene derivatives were studied to investigate the scope and limitations of this novel cyclisation process. The model substrates studied demonstrate that the samarium ketyl cyclisations are essentially restricted to the formation of six-membered rings. The diastereoselectivity of these reactions is strongly influenced by the connection of the alkyl side chain to the naphthalene core. ,-Naphth-1-yl-substituted ketones furnished cyclisation products, such as 17 or 22,26, as single diastereomers, whereas ,-naphth-2-yl-substituted precursors gave mixtures of diastereomers,as demonstrated by the conversion of model compound 10 into tricyclic products 18,a/18,b, or that of cyclohexanone derivative 33 into tetracyclic diastereomers 34,a/34,b. Cyclic ketones as ketyl precursors furnished steroid-like tetracyclic skeletons; however, due to the cis/cis fusion of rings B/C and C/D these products have an "unnatural" bowl-like shape. Several of the cyclisation products have been identified by X-ray analyses, which not only proved the constitutions, but also the relative configurations and the preferred conformations. Steroid analogue 23 was subjected to subsequent transformations, which demonstrate that the styrene-like double bond of such compounds can be used for further structural diversification. First attempts to synthesise related azasteroids by incorporating nitrogen atoms into the ketone moiety are also reported. Thus, pyrrolidine derivatives 44 and 47 as well as piperidine derivatives 50 and 52 were subjected to samarium diiodide induced cyclisations. The expected tetracyclic products 48, 49,a/49,b, 51 and 53,a/53,b were obtained in moderate to good yields. The stereoselectivities observed follow the rules already established for the all-carbon precursors. The resulting products, bearing a nitrogen atom in ring D, are interesting azasteroid analogues with "unnatural" configuration. [source] | |||||||||||||