Search results for "Silanes"
showing 10 items of 51 documents
Chemoselektive mono- und disilyletherbildung aus tertiären und sekundären silanen
1985
Abstract Tertiary and secondary silanes are O-selective. With alcohols the corresponding silyl ethers are formed. Cesium fluoride/imidazole (CsF/Im) is a better activating system than CsF alone. Primary OH groups are silylated remarkably faster under CsF/Im activation than secondary OH groups. Tertiary alcohols do not react. Primary OH groups are selectively protected also in the presence of secondary OH groups by silanes with bulky ligands such as triisopropylsilane ((i-Pr) 3 SiH ( 4 )). Ketones are neither reduced to silyl ethers nor transformed to silylenol ethers under the conditions employed. Secondary silanes form monosilyl ethers by amine activation; with CsF the formation of disilyl…
Non-degenerate 1,2-silyl shift in silyl substituted alkyltrimethylcyclopentadienes
2005
Abstract The five new silanes C5Me3RSiMenCl3 − n (n = 3, R = i-Pr (5); n = 2, R = i-Pr (6); n = 2, R = s-Bu (7); n = 2, R = cyclohexyl (8); and n = 3, R = t-Bu (9)) were synthesized by reaction of 1-alkyl-2,3,4-trimethylcyclopentadienyl lithium salts with appropriate chlorosilane and characterized by NMR, MS, and IR spectra. At elevated temperatures (250–360 K), all the silanes undergo a non-degenerate sigmatropic silyl rearrangement, which generates non-equivalent structures a and b. The presence of minor structure c was observed in compounds 5 and 7 only. The Diels–Alder cycloaddition of 5 with strong dienophiles tetracyanoethylene (TCNE), and dimethylacetylenedicarboxylate (DMAD) provide…
Reactions of titanocene-bis(trimethylsilyl)ethyne complexes with diethynylsilane derivatives
2001
Titanocene complexes [Ti(η 5 -C 5 H 5− n Me n ) 2 (η 2 -Me 3 SiCCSiMe 3 )] ( n =0, 4 and 5) react uniformly with siladiynes R 2 2 Si(CCR 1 ) 2 , where R 1 =Ph, and R 2 =Ph or Me, at elevated temperature in hydrocarbon solvents to give the corresponding silacyclobutene-annelated titanacyclobutene complexes, 3-bis(η 5 -cyclopentadienyl)titana-6-diorganylsilabicyclo[2.2.0]hexa-1(2),4(5)-dienes, [(η 5 -C 5 H 5− n Me n ) 2 Ti{R 1 2 C 4 (SiR 2 2 )}]. Products arising from [Ti(η 5 -C 5 H 5− n Me n ) 2 (η 2 -Me 3 SiCCSiMe 3 )] ( n =0, 2 (1,3-isomer), 4 and 5) and Me 2 Si(CCCMe 3 ) 2 vary with n : the non-methylated titanocene complex affords a mixture of an analogous silacyclobutene-annelated t…
Formation of silicones mediated by the sponge enzyme silicatein-α
2010
The sponge-restricted enzyme silicatein-α catalyzes in vivo silica formation from monomeric silicon compounds from sea water (i.e. silicic acid) and plays the pivotal role during synthesis of the siliceous sponge spicules. Recombinant silicatein-α, which was cloned from the demosponge Suberites domuncula (phylum Porifera), is shown to catalyze in vitro condensation of alkoxy silanes during a phase transfer reaction at neutral pH and ambient temperature to yield silicones like the straight-chained polydimethylsiloxane (PDMS). The reported condensation reaction is considered to be the first description of an enzymatically enhanced organometallic condensation reaction.
Apposition of silica lamellae during growth of spicules in the demosponge Suberites domuncula: Biological/biochemical studies and chemical/biomimetic…
2006
Recently it has been discovered that the formation of the siliceous spicules of Demospongiae proceeds enzymatically (via silicatein) and occurs matrix guided (on galectin strings). In addition, it could be demonstrated that silicatein, if immobilized onto inorganic surfaces, provides the template for the synthesis of biosilica. In order to understand the formation of spicules in the intact organism, detailed studies with primmorphs from Suberites domuncula have been performed. The demosponge spicules are formed from several silica lamellae which are concentrically arranged around the axial canal, harboring the axial filament composed of silicatein. Now we show that the appositional growth o…
Extent of the influence of phosphate buffer and ionic liquids on the reduction of the silanol effect in a C18 stationary phase
2017
The presence of anionic free silanols in the silica-based stationary phases gives rise to broad and asymmetrical peaks when cationic basic compounds are chromatographed using hydro-organic mobile phases. The addition to the mobile phase of a reagent with ionic character prevents the access of analytes to the free silanols, improving the peak shape. The silanol activity can be affected by the buffer concentration and mobile phase pH, factors that are not always considered sufficiently in the literature. In this work, the chromatographic behaviour of three basic β-adrenoceptor antagonists (acebutolol, nadolol and timolol), using mobile phases containing acetonitrile, was examined at different…
Diastereoselective Intramolecular Additions of Allyl- and Propargylsilanes to Iminium Ions: Synthesis of Cyclic and Bicyclic Quaternary Amino Acids
2010
Chiral imino lactones derived from (R)-phenylglycinol containing an allyl- or propargyltrimethylsilyl group in the side chain readily cyclized in the presence of acidic reagents to afford spirocyclic compounds with high diastereoselectivity. Removal of the chiral auxiliary produced 2-substituted 1-aminocycloalkanecarboxylic acids, whereas further cyclizations by means of metathesis or hydroamination reactions led to bicyclic derivatives of pipecolic acid and proline.
Streptavidin-coated TiO2 surfaces are biologically inert: Protein adsorption and osteoblast adhesion studies
2011
Non-fouling TiO2 surfaces are attractive for a wide range of applications such as biosensors and medical devices, where biologically inert surfaces are needed. Typically, this is achieved by controlled surface modifications which prevent protein adsorption. For example, polyethylene glycol (PEG) or PEG-derived polymers have been widely applied to render TiO2 surfaces biologically inert. These surfaces have been further modified in order to achieve specific bio-activation. Therefore, there have been efforts to specifically functionalize TiO2 surfaces with polymers with embedded biotin motives, which can be used to couple streptavidin for further functionalization. As an alternative, here a s…
The role of the dual nature of ionic liquids in the reversed-phase liquid chromatographic separation of basic drugs.
2010
The cationic nature of basic drugs gives rise to broad asymmetrical chromatographic peaks with conventional C18 columns and hydro-organic mixtures, due to the ionic interaction of the positively charged solutes with the free silanol groups on the alkyl-bonded reversed-phase packing. Ionic liquids (ILs) have recently attracted some attention to reduce this undesirable silanol activity. ILs are dual modifiers (with a cationic and anionic character), which means that both cation and anion can be adsorbed on the stationary phase, giving rise to interesting interactions with the anionic free silanols and the cationic basic drugs. A comparative study of the performance of four imidazolium-based I…
Fundamental Insights into the Covalent Silane Functionalization of NiFe Layered Double Hydroxides
2020
Layered double hydroxides (LDHs) are a class of 2D anionic materials exhibiting wide chemical versatility and promising applications in different fields, ranging from catalysis to energy storage and conversion. However, the covalent chemistry of this kind of 2D materials is still barely explored. Herein, the covalent functionalization with silanes of a magnetic NiFe-LDH is reported. The synthetic route consists of a topochemical approach followed by anion exchange reaction with surfactant molecules prior to covalent functionalization with the (3-aminopropyl)triethoxysilane (APTES) molecules. The functionalized NiFe-APTES was fully characterized by X-ray diffraction, infrared spectroscopy, e…