A Convenient and Efficient Rhenium‐Catalyzed Hydrosilylation of Ketones and Aldehydes

Dong, Hailin; Berke, Heinz

doi:10.1002/adsc.200900246

Cited by 38 publications

(19 citation statements)

References 45 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Catalytic systems based on rhodium, 54 rhenium, 55 nickel, 56 and copper, 26 can carry out these reactions. Catalytic systems based on rhodium, 54 rhenium, 55 nickel, 56 and copper, 26 can carry out these reactions.…”

Section: Catalytic Testing In Hydrosilylation Reactionsmentioning

confidence: 99%

Synthesis and characterisation of an N-heterocyclic carbene with spatially-defined steric impact

2016

View full text Add to dashboard Cite

The synthesis and co-ordination chemistry of a new 'bulky yet flexible' N-heterocyclic carbene ("IPaul") is reported. This carbene has spatially-defined steric impact; steric maps show that two quadrants are very bulky while the other two are quite open. The electronic properties of this carbene are very similar to those of other 1,3-diarylimidazol-2-ylidenes. Copper, silver, iridium, and nickel complexes of the new ligand have been prepared. In solution, the ligand adopts two different conformations, while X-ray crystallographic analyses of the transition metal complexes suggest that the syn-conformer is preferred in the solid state due to intermolecular interactions. The copper(i) chloride complex of this new ligand has been shown to be highly-active in the hydrosilylation of carbonyl compounds, when compared to the analogous IPr, IMes, IPr* and IPr*(OMe) complexes.

show abstract

Section: Catalytic Testing In Hydrosilylation Reactionsmentioning

confidence: 99%

Synthesis and characterisation of an N-heterocyclic carbene with spatially-defined steric impact

2016

View full text Add to dashboard Cite

show abstract

“…Hydrosilylation of unsaturated bonds such as alkenes [1], alkynes [2] and carbonyls [3] is one of the more important processes involving organosilanes. Transition metal complexes containing iron [4,5], tungsten [6], molybdenum [7], manganese [8,9]], rhenium [10,11], rhodium [12], silver [13], nickel [14], and most recently ruthenium [2,15,16] have been used to catalyse such processes.…”

Section: Introductionmentioning

confidence: 99%

Ruthenium carbonyl-catalysed Si–heteroatom X coupling (X = S, O, N)

Toh

Poh

Lim

et al. 2012

Journal of Organometallic Chemistry

View full text Add to dashboard Cite

“…[73][74][75] An initial trial NMR reaction with benzaldehyde was carried out using the standard reaction conditions of 1.2 eq. of PhSiH 3 , 0.5 mL of CD 3 CN and 2.5 mol% of 2 at 80°C.…”

Section: Reduction Of Aldehydes and Ketonesmentioning

confidence: 99%

Reduction of carbon dioxide and organic carbonyls by hydrosilanes catalysed by the perrhenate anion

Morris

Weetman

Wennmacher

et al. 2017

Catal. Sci. Technol.

View full text Add to dashboard Cite

aThe simple perrhenate salt [NĲhexyl) 4 ]ĳ(ReO 4 )] acts as a catalyst for the reduction of organic carbonyls and carbon dioxide by primary and secondary hydrosilanes. In the case of CO 2 , this results in the formation of methanol equivalents via silylformate and silylacetal intermediates. Furthermore, the addition of alkylamines to the reaction mixture favours catalytic amine N-methylation over methanol production under certain conditions. DFT analysis of the mechanism of CO 2 reduction shows that the perrhenate anion activates the silylhydride forming a hypervalent silicate transition state such that the CO 2 can directly cleave a Si-H bond. IntroductionThe hydrosilylation of CO 2 to silylformates and silylethers is an attractive route for CO 2 utilisation as, unlike hydrogenation, this reaction is exergonic due to the comparative ease of Si-H bond activation and the strength of the Si-O bond, and the availability of relatively inexpensive and environmentally benign hydrosilanes. 66 Important to this chemistry is the formation of a lipophilic ion pair in which electrostatic and hydrogen-bonding interactions are enhanced in the hydrophobic phase. This catalyst has the advantages of ease of synthesis and manipulation and lack of air-sensitivity, and the recovery of the precious metal is driven by straightforward reverse phase-transfer. Given the efficacy of this new catalyst system and the use of high oxidation state rhenium oxo complexes in reduction catalysis, it is shown here that perrhenate can act as a catalyst for the reduction of carbon dioxide to methanol equivalents by hydrosilanes, that the methylation of alkylamines using CO 2 as the C 1 source occurs under similar catalytic conditions, and that this method can be used to reduce aldehydes and ketones to silylalcohols. Results and discussion Reduction of carbon dioxideInitially, the reaction between CO 2 (2.5 bar), PhSiH 3 (2.0 mmol), and pyridinium perrhenate 1 (2.0 mol%) at 80°C in C 6 D 6 in a Teflon-tapped NMR tube was monitored by 1 H NMR spectroscopy. However, only 15% consumption of hydrosilane is seen under these conditions after 16 h ( Fig. S2 and S3, ESI †). In contrast, when the reaction is carried out using the simple lipophilic quaternary ammonium salt [NĲhexyl) 4 ]ĳReO 4 ] 2 (2.5 mol%) with PhSiH 3 in C 6 D 6 at 1 bar of

show abstract

A Convenient and Efficient Rhenium‐Catalyzed Hydrosilylation of Ketones and Aldehydes

Cited by 38 publications

References 45 publications

Synthesis and characterisation of an N-heterocyclic carbene with spatially-defined steric impact

Synthesis and characterisation of an N-heterocyclic carbene with spatially-defined steric impact

Ruthenium carbonyl-catalysed Si–heteroatom X coupling (X = S, O, N)

Reduction of carbon dioxide and organic carbonyls by hydrosilanes catalysed by the perrhenate anion

Contact Info

Product

Resources

About