Hydrosilylation reactions of functionalized alkenes

Naganawa, Yuki; Inomata, Kohei; Satō, Kazuhiko; Nakajima, Yumiko

doi:10.1016/j.tetlet.2019.151513

Cited by 57 publications

(42 citation statements)

References 85 publications

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“…The hydrosilylation reaction is an important reaction in the arsenal of organic practitioners and can be considered as a strategic transformation in bulk chemistry and silicon industry. This reaction, involving silanes and commodity alkenes or alkynes, is often catalyzed by expensive transition metals (e. g., platinum‐based Speier's and Karstedt's catalysts), [4] although significant contributions were brought to develop earth‐abundant transition metal catalysts (e. g., Ni, Fe, Co, Mn) [5] . Indeed, there is a high demand in developing efficient hydrosilylation reactions using inexpensive transition metal catalysts to offer economical alternative to the existing manufacturing processes.…”

Section: Methodsmentioning

confidence: 99%

Copper‐Photocatalyzed Hydrosilylation of Alkynes and Alkenes under Continuous Flow

Zhong

Pannecoucke

Jubault

et al. 2021

Chemistry A European J

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Herein, the photocatalytic hydrosilylation of alkynes and alkenes under continuous flow conditions is described. By using 0.2 mol % of the developed [Cu(dmp)(XantphosTEPD)]PF6 under blue LEDs irradiation, a large panel of alkenes and alkynes was hydrosilylated in good to excellent yields with a large functional group tolerance. The mechanism of the reaction was studied, and a plausible scenario was suggested.

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Section: Methodsmentioning

confidence: 99%

Copper‐Photocatalyzed Hydrosilylation of Alkynes and Alkenes under Continuous Flow

Zhong

Pannecoucke

Jubault

et al. 2021

Chemistry A European J

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“…Therefore, we focused on the preparation of an ethylene-bridged polysilsesquioxane film by hydrosilylation as a powerful tool for the formation of SiCCSi bonds. 41 We designed a synthetic route shown in Scheme 1 for the preparation of oligomethylsilsesquioxanes having hydrosilyl and vinyl groups as precursors of the ethylene-bridged polysilsesquioxane film. First, according to a modified reported procedure, 42,43 the sol−gel reaction of triethoxymethylsilane was performed to achieve the complete hydrolysis of the ethoxy groups and to ensure a high content of silanol groups for the capping reaction.…”

Section: ■ Introductionmentioning

confidence: 99%

Crack- and Shrinkage-Free Ethylene-Bridged Polysilsesquioxane Film Prepared by a Hydrosilylation Reaction

et al. 2021

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With the aim of developing an improved strategy for the preparation of ethylene-bridged polysilsesquioxanes as thermal insulator materials, this paper describes the synthesis of a crack- and shrinkage-free ethylene-bridged polysilsesquioxane film by the hydrosilylation reaction of hydrodimethyl-silylated oligomethylsilsesquioxane (MSQ-SiH) and dimethylvinyl-silylated oligomethylsilsesquioxane (MSQ-SiVi) in the presence of Karstedt’s catalyst. Polysilsesquioxane precursors were prepared by the sol–gel reaction of triethoxymethylsilane and the successive capping reaction with chlorodimethylsilane and chlorodimethylvinylsilane. The obtained ethylene-bridged polysilsesquioxane film showed lower density and thermal diffusivity (1.13 g/cm3 and 1.15 × 10–7 m2/s, respectively) than a polymethylsilsesquioxane film (1.34 g/cm3 and 1.36 × 10–7 m2/s, respectively). As a result of the introduction of the SiCCSi ethylene bridge, the thermal insulation property of the polysilsesquioxane film was enhanced.

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“…Silanes, especially polymethylhydrosiloxane (PMHS), can be regarded as an ideal substitute for hydrogen in the liquid-phase hydrodeoxygenation reaction due to its low-cost and easy availability. , Moreover, the Si–H bond in silanes is weaker than the nonpolar H–H bond in H 2 , and thereby the Si–H bond in silanes is more easily dissociated to produce reactive hydrogen protons for HDO, which makes the HDO reaction take place under mild conditions with better chemoselectivity compared with the traditional HDO method. To date, several catalytic protocols employing PMHS as the reducing agent have been developed for the selective deoxygenation of the carbonyl compounds to alkenes in the presence of platinum (Pt) and palladium (Pd) based catalysts. − Chouthaiwale et al investigated the Pd salts as highly effective catalysts for selectively reducing the aryl ketones and aldehydes in DMF as the solvent and triethylsilane as the hydride source, and the corresponding benzylic alcohols could be obtained in excellent yields. Unfortunately, these reported publications concern mostly homogeneous metal complexes as catalysts, which hinders the reusability of the catalysts and the purification of the products.…”

Section: Introductionmentioning

confidence: 99%

Controlled Hydrodeoxygenation of Biobased Ketones and Aldehydes over an Alloyed Pd–Zr Catalyst under Mild Conditions

Ding

Zong

et al. 2021

ACS Sustainable Chem. Eng.

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The substitution of green hydrogen donors for replacing high-pressure H 2 to achieve biomass derived ketone and aldehyde hydrodeoxygenation (HDO) under mild conditions has attracted widespread attention. However, it remains a considerable challenge to get rid of acid additives and control product selectivity. Herein, a series of bimetallic Pd−M/HZSM-5 catalysts (M = Zr, Mn, Zn, or La) were fabricated for controlled hydrodeoxygenation of biobased ketones and aldehydes (acetophenone, benzophenone, 4-hydroxyacetophenone, vanillin, furfural) using polymethylhydrosiloxane (PMHS) as the green H-donor, in which >99% conversion and >99% selectivity to ethylbenzene were achieved for hydrodeoxygenation of acetophenone as the probe within 3 h at 35 °C over the as-prepared 0.5%Pd−2.0%Zr/HZSM-5 catalyst with a Pd/ Zr mass ratio of 1:4. According to characterizations of TEM-HAADF, XPS, ESR, and H 2 -TPR, the Pd−Zr alloy structure was formed on the bimetallic Pd−Zr/HZSM-5 catalyst, promoting the transform of Pd−O−Zr solid solution to PdO−ZrO 2 and the generation of oxygen vacancy. Moreover, the abundant of oxygen vacancies on the alloyed Pd−Zr/HZSM-5 catalysts enhance the dissociation of silanes to provide the abundance of hydrogen protons, greatly accelerating the hydrogenation of biobased ketones and aldehydes, and then the acid site of the Pd−Zr/HZSM-5 catalyst promotes the dehydration of the intermediates (alcohols) to hydrocarbons. Furthermore, the as-fabricated Pd−Zr/HZSM-5 alloy catalyst can achieve an excellent recycling capability after six uses and exhibits universality toward various biobased ketones and aldehydes at 35 °C. The present findings provide new insights into the design of selective HDO of biomass in a green process.

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Hydrosilylation reactions of functionalized alkenes

Cited by 57 publications

References 85 publications

Copper‐Photocatalyzed Hydrosilylation of Alkynes and Alkenes under Continuous Flow

Copper‐Photocatalyzed Hydrosilylation of Alkynes and Alkenes under Continuous Flow

Crack- and Shrinkage-Free Ethylene-Bridged Polysilsesquioxane Film Prepared by a Hydrosilylation Reaction

Controlled Hydrodeoxygenation of Biobased Ketones and Aldehydes over an Alloyed Pd–Zr Catalyst under Mild Conditions

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