Synthesis and reactivity of bis(triethoxysilyl)methane, tris(triethoxysilyl)methane and some derivatives

Corriu, Robert J. P.; Granier, Michel; Lanneau, G. F.

doi:10.1016/s0022-328x(98)00365-9

Cited by 29 publications

(24 citation statements)

References 81 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…31 Earlier, though not on PMO‐materials, Corriu showed that the precursor bis(triethoxysilyl)methane can be deprotonated due to the negative hyperconjugation of the molecular orbitals of the two CH bonds with the antibonding σ* orbitals at the silicon atom. The resulting anion can react with a variety of electrophiles according to nucleophilic substitution reactions 32…”

Section: Hierarchical Features Of Mesoporous Silica Materials As Protmentioning

confidence: 99%

Selective Photocatalytic Oxidation of Alcohols to Aldehydes in Water by TiO₂ Partially Coated with WO₃

Tsukamoto

Ikeda

Shiraishi

et al. 2011

Chemistry A European J

104

View full text Add to dashboard Cite

Semiconductor TiO(2) particles loaded with WO(3) (WO(3)/TiO(2)), synthesized by impregnation of tungstic acid followed by calcination, were used for photocatalytic oxidation of alcohols in water with molecular oxygen under irradiation at λ>350 nm. The WO(3)/TiO(2) catalysts promote selective oxidation of alcohols to aldehydes and show higher catalytic activity than pure TiO(2). In particular, a catalyst loading 7.6 wt % WO(3) led to higher aldehyde selectivity than previously reported photocatalytic systems. The high aldehyde selectivity arises because subsequent photocatalytic decomposition of the formed aldehyde is suppressed on the catalyst. The TiO(2) surface of the catalyst, which is active for oxidation, is partially coated by the WO(3) layer, which leads to a decrease in the amount of formed aldehyde adsorbed on the TiO(2) surface. This suppresses subsequent decomposition of the aldehyde on the TiO(2) surface and results in high aldehyde selectivity. The WO(3)/TiO(2) catalyst can selectively oxidize various aromatic alcohols and is reusable without loss of catalytic activity or selectivity.

show abstract

Section: Hierarchical Features Of Mesoporous Silica Materials As Protmentioning

confidence: 99%

Selective Photocatalytic Oxidation of Alcohols to Aldehydes in Water by TiO₂ Partially Coated with WO₃

Tsukamoto

Ikeda

Shiraishi

et al. 2011

Chemistry A European J

104

View full text Add to dashboard Cite

show abstract

“…Hyperconjugative n O → σ SiX * interactions (cf., the α effect) are primarily responsible for the increased torsional flexibility and diminished basicity of silicones and thus contribute strongly to their broad application range . Last, organic trichlorosilyl and trialkoxysilyl derivatives represent key starting materials for the preparation of silsesquioxanes and other hybrid organic–inorganic macromolecules, which find applications as surface coatings, catalyst supports, xerogels, ceramic precursors, and optoelectronic materials. − …”

Section: Introductionmentioning

confidence: 99%

Exhaustively Trichlorosilylated C₁ and C₂ Building Blocks: Beyond the Müller–Rochow Direct Process

Georg¹,

Teichmann²,

Bursch

et al. 2018

J. Am. Chem. Soc.

View full text Add to dashboard Cite

The Cl-induced heterolysis of the Si-Si bond in SiCl generates an [SiCl] ion as reactive intermediate. When carried out in the presence of CCl or ClC═CCl (CHCl solutions, room temperature or below), the reaction furnishes the monocarbanion [C(SiCl)] ([A]; 92%) or the vicinal dianion [(ClSi)C-C(SiCl)] ([B]; 85%) in excellent yields. Starting from [B], the tetrasilylethane (ClSi)(H)C-C(H)(SiCl) (HB) and the tetrasilylethene (ClSi)C═C(SiCl) (B; 96%) are readily available through protonation (CFSOH) or oxidation (CuCl), respectively. Equimolar mixtures of HB/[B] or B/[B] quantitatively produce 2 equiv of the monoanion [HB] or the blue radical anion [B], respectively. Treatment of B with Cl ions in the presence of CuCl furnishes the disilylethyne ClSiC≡CSiCl (C; 80%); in the presence of [HMeN]Cl, the trisilylethene (ClSi)C═C(H)SiCl (D; 72%) is obtained. Alkyne C undergoes a [4+2]-cycloaddition reaction with 2,3-dimethyl-1,3-butadiene (CHCl, 50 °C, 3d) and thus provides access to 1,2-bis(trichlorosilyl)-4,5-dimethylbenzene (E1; 80%) after oxidation with DDQ. The corresponding 1,2-bis(trichlorosilyl)-3,4,5,6-tetraphenylbenzene (E2; 83%) was prepared from C and 2,3,4,5-tetraphenyl-2,4-cyclopentadien-1-one under CO extrusion at elevated temperatures (CHCl, 180 °C, 4 d). All closed-shell products were characterized by H,C{H}, and Si NMR spectroscopy; an EPR spectrum of [ nBuN][B] was recorded. The molecular structures of [ nBuN][A], [ nBuN][B], B, E1, and E2 were further confirmed by single-crystal X-ray diffraction. On the basis of detailed experimental investigations, augmented by quantum-chemical calculations, plausible reaction mechanisms for the formation of [A], [B], C, and D are postulated.

show abstract

“…The concept is portrayed in Figure 1 . A parent drug molecule containing a reactive hydroxyl group is converted to its tetraalkoxysilane (the silicate derivative) by reaction with a trialkoxychlorosilane 9 derivatizing agent. 10 Eventual hydrolytic cleavage returns the parent drug.…”

Section: Introductionmentioning

confidence: 99%

Silicate Esters of Paclitaxel and Docetaxel: Synthesis, Hydrophobicity, Hydrolytic Stability, Cytotoxicity, and Prodrug Potential

et al. 2014

View full text Add to dashboard Cite

We report here the synthesis and selected properties of various silicate ester derivatives (tetraalkoxysilanes) of the taxanes paclitaxel (PTX) and docetaxel (DTX) [i.e., PTX-OSi(OR)3 and DTX-OSi(OR)3]. Both the hydrophobicity and hydrolytic lability of these silicates can be (independently) controlled by choice of the alkyl group (R). The synthesis, structural characterization, hydrolytic reactivity, and in vitro cytotoxicity against the MDA-MB-231 breast cancer cell line of most of these derivatives are described. We envision that the greater hydrophobicity of these silicates (vis-à-vis PTX or DTX itself) should be advantageous from the perspective of preparation of stable aqueous dispersions of amphiphilic block-copolymer-based nanoparticle formulations.

show abstract

Synthesis and reactivity of bis(triethoxysilyl)methane, tris(triethoxysilyl)methane and some derivatives

Cited by 29 publications

References 81 publications

Selective Photocatalytic Oxidation of Alcohols to Aldehydes in Water by TiO₂ Partially Coated with WO₃

Selective Photocatalytic Oxidation of Alcohols to Aldehydes in Water by TiO₂ Partially Coated with WO₃

Exhaustively Trichlorosilylated C₁ and C₂ Building Blocks: Beyond the Müller–Rochow Direct Process

Silicate Esters of Paclitaxel and Docetaxel: Synthesis, Hydrophobicity, Hydrolytic Stability, Cytotoxicity, and Prodrug Potential

Contact Info

Product

Resources

About

Synthesis and reactivity of bis(triethoxysilyl)methane, tris(triethoxysilyl)methane and some derivatives

Cited by 29 publications

References 81 publications

Selective Photocatalytic Oxidation of Alcohols to Aldehydes in Water by TiO2 Partially Coated with WO3

Selective Photocatalytic Oxidation of Alcohols to Aldehydes in Water by TiO2 Partially Coated with WO3

Exhaustively Trichlorosilylated C1 and C2 Building Blocks: Beyond the Müller–Rochow Direct Process

Silicate Esters of Paclitaxel and Docetaxel: Synthesis, Hydrophobicity, Hydrolytic Stability, Cytotoxicity, and Prodrug Potential

Contact Info

Product

Resources

About

Selective Photocatalytic Oxidation of Alcohols to Aldehydes in Water by TiO₂ Partially Coated with WO₃

Selective Photocatalytic Oxidation of Alcohols to Aldehydes in Water by TiO₂ Partially Coated with WO₃

Exhaustively Trichlorosilylated C₁ and C₂ Building Blocks: Beyond the Müller–Rochow Direct Process