18388-85-7Relevant academic research and scientific papers
Dicarbonylative benzannulation of 3-acetoxy-1,4-enynes with CO and silylboranes by Pd and Cu cooperative catalysis: One-step access to 3-hydroxyarylacylsilanes
Wu, Li-Jun,Yang, Liang-Feng,Li, Jin-Heng,Wang, Qiu-An
, p. 1669 - 1672 (2020)
A new, general Pd/Cu-cocatalysed dicarbonylative benzannulation of 3-acetoxy-1,4-enynes with CO and silylboranes is described. The method utilizes CO as both a one-carbon (C1) unit and an external addition functional reagent to achieve an unprecedented dicarbonylative benzannulation process, and represents a facile, efficient route to 3-hydroxyarylacylsilanes. Mechanistically, the silyl-Cu intermediate formed from CuF2 and silylboranes, and silyl-Pd intermediate generated by transmetallation are two key factors for successfully targeting the reaction and selectivity.
An efficient methyltrioxorhenium(VII)-catalyzed transformation of hydrotrioxides (ROOOH) into dihydrogen trioxide (HOOOH)
Bergant, Ana,Cerkovnik, Janez,Plesnicar, Bozo,Tuttle, Tell
, p. 14086 - 14087 (2008)
Dihydrogen trioxide (HOOOH) is formed nearly quantitatively in the low-temperature (-70 °C) methyltrioxorhenium(VII) (MTO)-catalyzed transformation of silyl hydrotrioxides (R3SiOOOH), and some acetal hydrotrioxides, in various solvents, as confirmed by 1H, and 17O NMR spectroscopy. The calculated energetics (B3LYP) for the catalytic cycle, using H3SiOOOH as a model system, is consistent with the experimentally observed activation energy (9.5 ± 2.0 kcal/mol) and a small kinetic solvent isotope effect (kH2O/kD2O = 1.1 ± 0.1), indicating an initial concerted reaction between the silyl hydrotrioxide and MTO in the rate-determining step. With the addition of water in the next step, the intermediate undergoes a σ-bond metathesis reaction to break the Re-OOOH bond and form HOOOH, together with the second dihydroxy intermediate. The final step in the catalytic cycle involves a second, catalytic water that lowers the barrier to form H3SiOH and MTO. Copyright
Copper-Containing Polyoxometalate-Based Metal-Organic Framework as a Catalyst for the Oxidation of Silanes: Effective Cooperative Catalysis by Metal Sites and POM Precursor
Ma, Xinyi,Jing, Zhen,Li, Kunhong,Chen, Yian,Li, Dandan,Ma, Pengtao,Wang, Jingping,Niu, Jingyang
supporting information, p. 4056 - 4061 (2022/03/03)
The oxidation of silanes into silanols is a very necessary transformation, and yet the rational fabrication of efficient catalysts for this reaction remains a challenging task. Here, a 3D polyoxometalate-based metal-organic framework (POMOF), [Cu3(pz)3{PMo12O40}]·H2O (HENU-8, HENU = Henan University; pz = pyrazine) was consciously prepared and first employed in the oxidation of dimethylphenylsilane with tert-butyl hydroperoxide (TBHP) as an oxidant, achieving 89% yield at a production rate of 132 mmol·g-1·h-1. Control experiments indicated that polyoxometalates and Cu atoms together affected the ultimate outcome in this catalytic system, and the designed catalyst followed a free radical mechanism.
Metal-free hydrogen evolution cross-coupling enabled by synergistic photoredox and polarity reversal catalysis
Cao, Jilei,Lu, Kanghui,Ma, Lishuang,Yang, Xiaona,Zhou, Rong
supporting information, p. 8988 - 8994 (2021/11/23)
A synergistic combination of photoredox and polarity reversal catalysis enabled a hydrogen evolution cross-coupling of silanes with H2O, alcohols, phenols, and silanols, which afforded the corresponding silanols, monosilyl ethers, and disilyl ethers, respectively, in moderate to excellent yields. The dehydrogenative cross-coupling of Si-H and O-H proceeded smoothly with broad substrate scope and good functional group compatibility in the presence of only an organophotocatalyst 4-CzIPN and a thiol HAT catalyst, without the requirement of any metals, external oxidants and proton reductants, which is distinct from the previously reported photocatalytic hydrogen evolution cross-coupling reactions where a proton reduction cocatalyst such as a cobalt complex is generally required. Mechanistically, a silyl cation intermediate is generated to facilitate the cross-coupling reaction, which therefore represents an unprecedented approach for the generation of silyl cationviavisible-light photoredox catalysis.
Selective Electrochemical Hydrolysis of Hydrosilanes to Silanols via Anodically Generated Silyl Cations
Liang, Hao,Wang, Lu-Jun,Ji, Yun-Xing,Wang, Han,Zhang, Bo
supporting information, p. 1839 - 1844 (2020/12/01)
The first electrochemical hydrolysis of hydrosilanes to silanols under mild and neutral reaction conditions is reported. The practical protocol employs commercially available and cheap NHPI as a hydrogen-atom transfer (HAT) mediator and operates at room temperature with high selectivity, leading to various valuable silanols in moderate to good yields. Notably, this electrochemical method exhibits a broad substrate scope and high functional-group compatibility, and it is applicable to late-stage functionalization of complex molecules. Preliminary mechanistic studies suggest that the reaction appears to proceed through a nucleophilic substitution reaction of an electrogenerated silyl cation with H2O.
Sterically encumbered tris(trialkylsilyl) phosphine precursors for quantum dot synthesis
Chandrasiri, Hashini B.,Kim, Eun Byoel,Snee, Preston T.
, p. 15928 - 15935 (2020/11/03)
The synthesis of nanomaterials with a narrow size distribution is challenging, especially for III-V semiconductor nanoparticles (also known as quantum dots). Concerning phosphides, this issue has been largely attributed the use of overly reactive precursors. The problem is exacerbated due to the narrow range of competent reagents for III-V semiconductor syntheses. We report the use of sterically encumbered tris(triethylsilyl) phosphine and tris(tributylsilyl) phosphine for InP quantum dot (QD) synthesis among others. The hypothesis was that these reagents are less reactive than the near-ubiquitous precursor tris(trimethylsilyl) phosphine and can be used to create more homogeneous materials. It was found that the InP products' quantum yields and emission color saturation (fwhm) were improved, but not to the levels realized in CdSe QDs. Regardless, these reagents have other positive attributes; they are less pyrophoric and can be applied toward the synthesis of II-V semiconductors and organophosphorus compounds. Concerning safe practices, we demonstrate that ammonium bifluoride is an effective replacement for highly toxic HF for the post-treatment of III-V semiconductor quantum dots.
Highly Selective Hydroxylation and Alkoxylation of Silanes: One-Pot Silane Oxidation and Reduction of Aldehydes/Ketones
Luo, Nianhua,Liao, Jianhua,Ouyang, Lu,Wen, Huiling,Zhong, Yuhong,Liu, Jitian,Tang, Weiping,Luo, Renshi
, p. 165 - 171 (2020/01/21)
An efficient chemoselective iridium-catalyzed method for the hydroxylation and alkoxylation of organosilanes to generate hydrogen gas and silanols or silyl ethers was developed. A variety of sterically hindered silanes with alkyl, aryl, and ether groups were tolerated. Furthermore, this atom-economical catalytic protocol can be used for the synthesis of silanediols and silanetriols. A one-pot silane oxidation and chemoselective reduction of aldehydes/ketones was also realized.
Selective Manganese-Catalyzed Oxidation of Hydrosilanes to Silanols under Neutral Reaction Conditions
Wang, Kaikai,Zhou, Jimei,Jiang, Yuting,Zhang, Miaomiao,Wang, Chao,Xue, Dong,Tang, Weijun,Sun, Huamin,Xiao, Jianliang,Li, Chaoqun
supporting information, p. 6380 - 6384 (2019/05/06)
The first manganese-catalyzed oxidation of organosilanes to silanols with H2O2 under neutral reaction conditions has been accomplished. A variety of organosilanes with alkyl, aryl, alknyl, and heterocyclic substituents were tolerated, as well as sterically hindered organosilanes. The oxidation appears to proceed by a concerted process involving a manganese hydroperoxide species. Featuring mild reaction conditions, fast oxidation, and no waste byproducts, the protocol allows a low-cost, eco-benign synthesis of both silanols and silanediols.
Synthesis, characterization and catalytic oxidation of organosilanes with a novel multilayer polyoxomolybdate containing mixed-valence antimony
Wang, Yaping,Lu, Jingkun,Ma, Xinyi,Niu, Yanjun,Singh, Vikram,Ma, Pengtao,Zhang, Chao,Niu, Jingyang,Wang, Jingping
, p. 167 - 174 (2018/04/24)
Oxidation of organosilanes is one of the pivotal reactions in organic synthesis and the corresponding products of silanols are widely as raw materials in industrial processes. In this paper, a new type of polyoxomolybdate containing mixed-valence antimony, [SbVSbIII4Mo18O66]7? (1a), has been isolated as tetramethyl ammonium salt in aqueous solution. The compound was structurally characterized by FT-IR, XPRD, TG, XPS, ESI–MS etc. It is the first time that the containing mixed-valence antimony polyoxomolybdate was used as a heterogeneous catalyst to efficaciously catalyze the oxidation of organosilanes to silanols under mild reaction conditions. Furthermore, the catalyst was stable and maintained its catalytic activity after three reaction cycles.
Wettability-Driven Palladium Catalysis for Enhanced Dehydrogenative Coupling of Organosilanes
Lin, Jian-Dong,Bi, Qing-Yuan,Tao, Lei,Jiang, Tao,Liu, Yong-Mei,He, He-Yong,Cao, Yong,Wang, Yang-Dong
, p. 1720 - 1727 (2017/08/15)
Direct coupling of Si-H bonds has emerged as a promising strategy for designing chemically and biologically useful organosilicon compounds. Heterogeneous catalytic systems sufficiently active, selective, and durable for dehydrosilylation reactions under mild conditions have been lacking to date. Herein, we report that the hydrophobic characteristics of the underlying supports can be advantageously utilized to enhance the efficiency of palladium nanoparticles (Pd NPs) for the dehydrogenative coupling of organosilanes. As a result of this prominent surface wettability control, the modulated catalyst showed a significantly higher level of efficiency and durability characteristics toward the dehydrogenative condensation of organosilanes with water, alcohols, or amines in comparison to existing catalysts. In a broader context, this work illustrates a powerful approach to maximize the performance of supported metals through surface wettability modulation under catalytically relevant conditions.
