The catalyzed hydrosilation reaction: substituent effects

Ab initio electronic structure calculations using MP2 wavefunctions have been used to investigate a reaction path for the hydrosilation reaction catalyzed by divalent titanium [modeled by TiH₂, TiCl₂, and Ti(C₅H₅)₂]. Optimized structures and energies are presented. All model reactions predict a barrierless reaction path compared to a barrier of 78 kcal/mol for the uncatalyzed reaction. Received: 11 August 1998 / Accepted: 3 September 1998 / Published online: 23 February 1999     

Synthesis and characterization of chemically bonded stationary phases on hydride surfaces by hydrosilation of alkynes and dienes

A hydrosilation reaction was used to bind four compounds with one or more alkyne groups or two alkene functionalities. The diffuse reflectance infrared Fourier transform, the 29Si cross-polarization magic-angle spinning (CP-MAS) NMR, and the 13C CP-MAS NMR spectra were used to characterize the various bonded materials. The bonded phase density was determined from carbon elemental analysis. The two ten-carbon hydrophobic stationary phases were characterized chromatographically and static stability tests were run in acidic and basic solutions.     

Geminal bond participation in the uncatalyzed Mukaiyama aldol reaction

We predicted that uncatalyzed Mukaiyama aldol reactions are under the control of the geminal bond participation. At the transition state of the model reaction, addition of CH₂O and CH₂CH(OSiH₃), the interbond energy IBE is negative between the σ-bonding orbital at the Z-position of the enolate terminal and , and positive between that at the E-position and . These results led us to predict that the electron-donating σ-bond at the Z-position enhances the reactivity. We calculated the enthalpies of activation of the reactions of a variety of the R-substituted silyl enolates and confirmed the prediction by showing that the reactivity of the Z-isomers relative to that of the E-isomers increases with the energy of the bonding orbital of the σ bond at the Z-position (the axial position at the transition state of the chair form). We demonstrate that the geminal bond participation is general not only to the pericyclic reactions but also to the aldol reaction, which is one of the most fundamental C-C bond forming reactions.     

Silica hydride intermediate for octadecylsilica and phenyl bonded phase preparation via heterogeneous hydrosilation in supercritical carbon dioxide

Investigations into the preparation of silica hydride intermediate in supercritical carbon dioxide (sc-CO(2)) that avoids the use of organic solvents such as toluene or dioxane are described. The effects of reaction temperature, pressure and time on the surface coverage of the supercritical fluid generated silica hydride intermediate were studied. Under optimised supercritical conditions of 120°C, 483 bar and 3 h reaction time, silica hydride (Si-H) conversion efficiencies of ca. 40% were achieved for the hydride intermediate prepared from a monofunctional silane reagent (dimethylmethoxysilane). Si-H conversion efficiencies (as determined from (29)Si CP-MAS NMR spectral analysis) for the hydride intermediate prepared from triethoxysilane (TES) in sc-CO(2) were found to be comparable to those obtained using a TES silanisation approach in an organic solvent. (13)C and (29)Si CP-MAS-NMR spectroscopy was employed to provide a complete structural assignment of the silica hydride intermediates. Furthermore, supercritical CO(2) was subsequently employed as a reaction medium for the heterogenous hydrosilation of silica hydride with octadecene and with styrene, in the presence of a free radical initiator. These supercritical fluid generated reversed-phase materials were prepared in a substantially reduced reaction time (3 h) compared to organic solvent based methods (100 h reaction time). Silica functionalisation in sc-CO(2) presents an efficient and clean alternative to organic solvent based methods for the preparation of important silica hydride intermediate and silica bonded stationary phases via a hydrosilation approach.     

Synthesis and characterization of a novel hydroxypolyether blocked polydimethylsiloxane PEO-b-PDMS-b-PEO

A novel hydroxypolyether blocked polydimethylsiloxane, poly（ethylene oxide） propyl-b-polydimethylsiloxane-b-propyl poly（ethylene oxide） （PEO-b-PDMS-b-PEO） was synthesized by simple hydrosilation reaction of poly（ethylene glycol） monoallyl ether with α,ω-dihydrogen terminated PDMS （HPDMS）. Fourier transform infrared spectroscopy （FTIR） and IH NMR were used to identify the structure of PEO-b-PDMS-b-PEO and intermediate product HPDMS. Based on the effect investigations of temperature, reactant molar ratio, catalyst and time on the hydrosilation, it was found that the conversion of Si-H bond to SiC bond increased with the increase of catalyst and time, and the reaction completed when the content of catalyst was 22μg/g and the time was 5 h, respectively. Urethane reaction of OH and NCO group confirms that PEO-b-PDMS-b-PEO is more reactive toward to diisocyanate than α,ω-dihydroxylbutyl terminated PDMS.     

Diels-Alder reaction of anthracene on carbosilane dendrimer

The dendritic macromolecule with 4, 8, 16 and 32 bicyclo end groups on the periphery has been created by the Diels-Alder reaction of anthracene and maleimide. The dendritic skeleton with triple bonds has been prepared by the hydrosilation and the alkynylation of bis(phenylethynyl)dimethylsilane as a core. The peripheral anthracene on dendrimers has been substituted by the reaction of chlorosilyl groups containing dendritic generations and 9-anthracenecarbinol. NMR and MALDI-TOF mass spectrum has characterized these Diels-Alder products.     

A review on synthetic approaches of heterocycles via insertion-cyclization reaction

Abstract

Heterocyclic compounds have a wide range of applications: they are predominant among the type of compounds used as pharmaceuticals, agrochemicals, fine chemicals, electronic components, polymers, and veterinary products. There is a vast scope to develop new heterocyclic compounds considering the high yield, low waste, and green synthesis. In this review, we have described the synthesis of heterocycles via insertion and cyclization which is achieved in recent years with the ideas, challenges, and milestone reactions.     

Synthesis of new tridentate chiral aminoalcohols by a multicomponent reaction and their evaluation as ligands for catalytic asymmetric Strecker reaction

A one-step, multicomponent Mannich-type reaction between phenols, paraformaldehyde, and β-aminoalcohols in the presence of LiCl afforded N-2-hydroxybenzyloxazolidines with high ortho-selectivity. Hydrolytic or reductive ring opening of the oxazolidines provided a series of N-salicyl-β-aminoalcohols in 84-92% overall yield. The synthesized compounds were evaluated as ligands for a titanium-catalyzed catalytic asymmetric Strecker reaction. The reaction employing 10 mol % of catalyst provided the Strecker products in excellent yields and up to 98% ee.     

乙酸烯丙酯的氢硅化反应

本文在对芳醛及环酮的氢硅化反应研究基础上, 进一步研究乙酸烯丙酯的氢硅化反应。(Ph~3P)~3RhCl作催化剂, 反应可在均相进行。采用假一级动力学方法, 以气相色谱法鉴测氢硅化产物生成的速率, 求得其反应速度常数, 进而分析其反应活性与反应物结构的关系, 并提出相应的可能机理。     

Synthesis and reactions of poly[(ethoxysilylene)phenylenevinylene]s and chain-to-pendant energy transfer in the resulting polymer

Reactions of (bromophenylethenyl)diethoxysilanes with magnesium in THF gave poly[(ethoxysilylene)phenylenevinylene]s. The ethoxy group of the polymers could be readily replaced with other substituents by treating them with nucleophiles. Optical properties of the resulting poly(silylenephenylenevinylene)s were examined with respect to their UV absorption and emission spectra. Of those, pyrenylethynyl-substituted one exhibited energy transfer from the backbone to the substituent in the photo-excited state.     

Application of dimeric orthopalladate complex of homoveratrylamine as an efficient catalyst in the Heck cross-coupling reaction

The [Pd{C₆H₂(CH₂CH₂NH₂)-(OMe)₂,3,4} (μ-Br)]₂ complex of homoveratrylamine was synthesized and its application in the Heck coupling reaction was studied. This complex had been demonstrated to be active and efficient catalyst for the Heck reaction of aryl iodides, bromides and even chlorides. The cross-coupled products were produced in excellent yields in a short reaction time using catalytic amounts of [Pd{C₆H₂(CH₂CH₂NH₂)-(OMe)₂,3,4} (μ-Br)]₂ complex in N-methyl-2-pyrrolidinone (NMP at 130 °C).     

A catalyst system for the reaction of carboxylic acids with aliphatic isocyanates

Catalysts have been found for the selective reaction of aliphatic isocyanates with carboxylic acids giving amides after carbon dioxide extrusion. Magnesium and calcium salts lead to a dramatic increase in reaction rates while improving the selectivity when sterically hindered isocyanates and/or carboxylic acids are used.     

Analysis of silica hydride and surface hydrosilation reactions by solid-state NMR in the preparation of<Emphasis Type="Italic"> p</Emphasis>-chlorobenzamide bonded silica phase

²⁹Si and ¹³C CP-MAS NMR spectroscopy was used to follow the conversion of native silica to a p-chlorobenzamide bonded silica material. The benzamide bonded phase was prepared via a hydrosilation reaction of a hydride silica intermediate with p-chloro-N-allylbenzamide. Solid-state NMR was used to show the disappearance of reactive surface hydride species (M_H) and to identify newly formed bonded chemical species on the silica surface. DRIFT spectroscopy, elemental analysis, and specific surface-area determinations (BET) of the prepared phases are also reported.     

Niobium pentachloride-silver perchlorate as an efficient catalyst in the Friedel-Crafts acylation and Sakurai-Hosomi reaction of acetals

Friedel-Crafts acylation catalyzed by niobium pentachloride with silver salt is described. Aromatic compounds with Ac₂O or Bz₂O were smoothly converted into the corresponding ketones in good to excellent yields. This system was also applied to the Sakurai-Hosomi reaction using acetals. The reaction proceeded quite rapidly to give the desired products in excellent yields.     

Study of catalytic effect of ammonium molybdate on the bisphthalonitrile resins curing reaction with aromatic amine

A kind of catalyst, ammonium molybdate was developed in this paper to promote the curing reaction of bisphthalonitrile resins with aromatic amine as curing agent, and the catalytic effect was studied by differential scanning calorimetry (DSC), rheometric measurements and thermogravimetric analysis (TGA). The results indicated that the catalyst could improve the curing rate and increase the curing degree, which could be regulated by the content of the catalyst used in the reaction.     

Application of dimeric cyclopalladated complex of tribenzylamine as an efficient catalyst in the Heck cross-coupling reaction

The activity of [Pd{C₆H₄(CH₂N(CH₂Ph)₂)} (μ-Br)]₂ complex was investigated in the Heck-Mizoroki C-C cross-coupling reaction. This complex is an active and efficient catalyst for the Heck reaction of aryl iodides, bromides and even chlorides and also arenesulfonyl chlorides. The cross-coupled products were produced in excellent yields in short reaction time using a catalytic amount of [Pd{C₆H₄(CH₂N(CH₂Ph)₂) (μ-Br)]₂ complex in NMP at 130 °C.     

用于电解水制氢的过渡金属有机骨架基催化剂

金属有机骨架(MOFs)材料因具有无机和有机的杂合性质、高度有序的多孔性、结构可修饰性、比表面积大和孔隙率高等特点,在催化领域具有广阔的应用前景。本文从氢能的开发利用角度出发,在纯MOFs、MOFs复合及衍生材料三个方面对近十年来过渡金属MOFs基催化剂在电解水制氢方面的重要研究进展进行了综述,着重针对材料的合成进行了探讨,以及在基础研究和产业应用的角度指出当前过渡金属MOFs基制氢催化剂面临的挑战和机遇,对其应用前景进行展望。     

Electrocatalyst design for promoting two-electron oxygen reduction reaction: Isolation of active site atoms

Selective two-electron (2 e^?) pathway oxygen reduction reaction (ORR) has gained prominence for enabling small-scale, on-site electrochemical H₂O₂ production and has emerged as a promising alternative to the conventional anthraquinone process. The rational design of catalysts that can suppress the competing four-electron pathway ORR is critical. This review highlights catalyst design strategies for promoting the selective 2 e^? pathway ORR, including alloying with inert metals, partial surface poisoning, and generating atomically dispersed sites. The major results and advances, as well as unresolved challenges are summarized.     

Reductive coupling reaction of aldehydes using indium(III) triflate as the catalyst

A reductive coupling reaction was effectively developed to convert an aldehyde to its symmetrical ether. The successful reactions required Et₃SiH and CH₂Cl₂ as the suitable solvent in the presence of a catalytic amount of In(OTf)₃. Various aldehydes were subjected to the method, and each afforded the expected ethers in good to excellent yields.     

以对-(4-烯丙氧基苯甲酰氧基)苯甲酸对-甲氧基苯酚酯为单体的液晶聚硅氧烷的合成与表征

侧链型液晶聚合物是目前很有兴趣的研究课题之一。在国内,有关的研究报道也逐渐增多,本工作设计并合成了对-(4-烯丙氧基苯甲酰氧基)苯甲酸对-甲氧基苯酚酯单体,其结构式为: