1516-80-9Relevant academic research and scientific papers
Synthesis of nitrogen and sulfur co-doped hierarchical porous carbons and metal-free oxidative coupling of silanes with alcohols
Chen, Bingfeng,Li, Fengbo,Mei, Qingqing,Yang, Youdi,Liu, Huizhen,Yuan, Guoqing,Han, Buxing
, p. 13019 - 13022 (2017)
Hierarchically porous N and S co-doped carbon was prepared by using 2,5-dihydroxy-1,4-benzoquinone as the carbon source, thiourea as the N and S source, and SiO2 particles as the template. Using the material as the catalyst, oxidative coupling of silanes with alcohols was conducted for the first time under metal-free conditions.
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.
Mechanistic Studies on the Hexadecafluorophthalocyanine–Iron-Catalyzed Wacker-Type Oxidation of Olefins to Ketones**
Grinenko, Vadim,Klau?, Hans-Henning,Kn?lker, Hans-Joachim,Puls, Florian,Seewald, Felix
supporting information, p. 16776 - 16787 (2021/11/04)
The hexadecafluorophthalocyanine–iron complex FePcF16 was recently shown to convert olefins into ketones in the presence of stoichiometric amounts of triethylsilane in ethanol at room temperature under an oxygen atmosphere. Herein, we describe an extensive mechanistic investigation for the conversion of 2-vinylnaphthalene into 2-acetylnaphthalene as model reaction. A variety of studies including deuterium- and 18O2-labeling experiments, ESI-MS, and 57Fe M?ssbauer spectroscopy were performed to identify the intermediates involved in the catalytic cycle of the oxidation process. Finally, a detailed and well-supported reaction mechanism for the FePcF16-catalyzed Wacker-type oxidation is proposed.
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.
N-Heterocyclic Olefin Catalyzed Silylation and Hydrosilylation Reactions of Hydroxyl and Carbonyl Compounds
Kaya, U?ur,Tran, Uyen P.N.,Enders, Dieter,Ho, Junming,Nguyen, Thanh V.
supporting information, p. 1398 - 1401 (2017/03/23)
N-Heterocyclic olefins (NHOs), the alkylidene derivatives of N-heterocyclic carbenes (NHCs), have recently emerged as a new family of promising organocatalysts with strong nucleophilicity and Br?nsted basicity. The development of a novel method is shown using NHOs as efficient promoters for the direct dehydrogenative silylation of alcohols or hydrosilylation of carbonyl compounds. Preliminary results of the first NHO-promoted asymmetric synthesis are also discussed.
Dehydrogenative Coupling of Hydrosilanes and Alcohols by Alkali Metal Catalysts for Facile Synthesis of Silyl Ethers
Harinath, Adimulam,Bhattacharjee, Jayeeta,Anga, Srinivas,Panda, Tarun K.
, p. 724 - 730 (2017/05/31)
Cross-dehydrogenative coupling (CDC) of hydrosilanes with hydroxyl groups, using alkali metal hexamethyldisilazide as a single-component catalyst for the formation of Si-O bonds under mild condition, is reported. The potassium salt [KN(SiMe3)2] is highly efficient and chemoselective for a wide range of functionalized alcohols (99% conversion) under solvent-free conditions. The CDC reaction of alcohols with silanes exhibits first-order kinetics with respect to both catalyst and substrate concentrations. The most plausible mechanism for this reaction suggests that the initial step most likely involves the formation of an alkoxide followed by the formation of metal hydride as active species.
Metal-Free Ammonium Iodide Catalyzed Oxidative Dehydrocoupling of Silanes with Alcohols
Yuan, Yan-Qin,Kumar, Pailla Santhosh,Guo, Sheng-Rong
supporting information, p. 1620 - 1623 (2017/08/11)
An ammonium iodide catalyzed direct oxidative coupling of silanes with alcohols to give various alkoxysilane derivatives was discovered. tert -Butyl hydroperoxide proved to be an efficient oxidant for this transformation. Attractive features of this protocol include its transition-metal-free nature and the mild reaction conditions.
Catalytic Dehydrogenative Coupling of Hydrosilanes with Alcohols for the Production of Hydrogen On-demand: Application of a Silane/Alcohol Pair as a Liquid Organic Hydrogen Carrier
Ventura-Espinosa, David,Carretero-Cerdán, Alba,Baya, Miguel,García, Hermenegildo,Mata, Jose A.
supporting information, p. 10815 - 10821 (2017/08/18)
The compound [Ru(p-cym)(Cl)2(NHC)] is an effective catalyst for the room-temperature coupling of silanes and alcohols with the concomitant formation of molecular hydrogen. High catalyst activity is observed for a variety of substrates affording quantitative yields in minutes at room temperature and with a catalyst loading as low as 0.1 mol %. The coupling reaction is thermodynamically and, in the presence of a Ru complex, kinetically favourable and allows rapid molecular hydrogen generation on-demand at room temperature, under air, and without any additive. The pair silane/alcohol is a potential liquid organic hydrogen carrier (LOHC) for energy storage over long periods in a safe and secure way. Silanes and alcohols are non-toxic compounds and do not require special handling precautions such as high pressure or an inert atmosphere. These properties enhance the practical applications of the pair silane/alcohol as a good LOHC in the automotive industry. The variety and availability of silanes and alcohols permits a pair combination that fulfils the requirements for developing an efficient LOHC.
Zinc Bis(triphenylsilyl) Stabilized by N-Heterocyclic Carbene
Lemmerz, Lara E.,Spaniol, Thomas P.,Okuda, Jun
, p. 1269 - 1274 (2016/11/23)
Triphenylsilylzinc compounds stabilized by an N-heterocyclic carbene, [Zn(SiPh3)2(IMes)] (2) and [ZnX(SiPh3)(IMes)] [X = Cl (3a), Br (3b), I (3c)] [IMes = 1,3-Bis(2,4,6-trimethylphenyl)imidazole-2-ylidene], were synthesized by transmetalation from [ZnX2(IMes)(THF)0–1] [X = Cl (1a), Br (1b), I (1c)] and [LiSiPh3(THF)3]. According to single-crystal X-ray diffraction, [Zn(SiPh3)2(IMes)] (2) shows a trigonal-planar coordinated central zinc atom, whereas [ZnCl(SiPh3)(IMes)(THF)] (3a-THF) shows a distorted tetrahedral coordination.
N-heterocyclic carbene organocatalysts for dehydrogenative coupling of silanes and hydroxyl compounds
Gao, Dongjing,Cui, Chunming
supporting information, p. 11143 - 11147 (2013/09/02)
Go organic! N-Heterocyclic carbene (NHC) 1,3-diisopropyl-4,5- dimethylimidazol-2-ylidene (IiPr) has been found to be an efficient and selective catalyst for the dehydrogenative coupling of a wide range of silanes and hydroxyl groups to form Si-O bonds under mild and solvent-free conditions (see scheme). Mechanistic studies indicated that the activation of hydroxyl groups by the NHC is the most plausible initial step for the process. Copyright
