KO2/crown ether: a novel catalytic system for the hydrosilation and Tishchenko reaction of aromatic aldehydes

Bideau, Franck Le; Coradin, Thibaud; Gourier, Didier; Henique, Josette; Samuel, Edmond

doi:10.1016/s0040-4039(00)00818-2

Cited by 18 publications

(4 citation statements)

References 8 publications

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“…A similar dependence has been observed with other catalysts, such as K 2 [Fe(CO) 4 ]/crown ether [35] and KO 2 /crown ether. [42] Therefore, substrates that contain electron-releasing groups on the aromatic ring have significantly lower TOFs. The lowest TOFs were observed if the substrate has an electron-releasing group with a donor atom, such as nitrogen, oxygen, or sulfur (entries 6 ± 8).…”

Section: Resultsmentioning

confidence: 99%

Homoleptic Lanthanide Amides as Homogeneous Catalysts for Alkyne Hydroamination and the Tishchenko Reaction

2001

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The homoleptic bis(trimethylsilyl)amides of Group 3 metals and lanthanides of the general type [Ln[N(SiMe3)2]3] (1) (Ln=Y, lanthanide) represent a new class of Tishchenko precatalysts and, to a limited extent, precatalysts for the hydroamination/cyclization of aminoalkynes. It is shown that 1 is the most active catalyst for the Tishchenko reaction. This contribution presents investigations on the scope of the reaction, substrate selectivity, lanthanide-ion size-effect, and kinetic/mechanistic aspects of the Tishchenko reaction catalyzed by 1. The turnover frequency is increased by the use of large-center metals and electron-withdrawing substrates. The reaction rate is second order with respect to the substrate. While donor atoms, such as nitrogen, oxygen, or sulfur, on the substrate decrease the turnover frequency, 1 shows a tolerance for a large number of functional groups. For the hydroamination/cyclization of aminoalkynes, 1 is less active than the well-known metallocene catalysts. On the other hand, 1 is much more readily accessible (one-step synthesis or commercially available), than the metallocenes and might therefore be an attractive alternative catalyst.

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Section: Resultsmentioning

confidence: 99%

Homoleptic Lanthanide Amides as Homogeneous Catalysts for Alkyne Hydroamination and the Tishchenko Reaction

2001

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“…In the course of our studies on the catalytic properties of BBC, we have recently demonstrated that the KO 2 -crown ether system was also an efficient catalyst for hydrosilylation reactions. 15 Such a system leads to stable superoxide O 2 Ϫ anion solutions in aprotic media. 16 O 2 Ϫ was reported to make a nucleophilic attack on various substrates.…”

Section: Discussionmentioning

confidence: 99%

Photoactivated formation of hydrogen spin adduct from phenylsilane. A new example of inverted spin trapping?

Coradin

Bideau

Henique

et al. 2000

J. Chem. Soc., Perkin Trans. 2

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Photodissociation of phenylsilane was studied by EPR spectroscopy using N-benzylidene-tert-butylamine N-oxide (PBN) and bis(benzene)chromium (BBC) as spin trapping systems. Under controlled UV irradiation and in the presence of dioxygen, hydrogen spin adducts were detected. Conditions for the formation and stability of the adducts have been studied. A mechanism involving "inverted spin trapping" was propounded that implies photoactivation of the spin traps followed by the formation of the superoxide radical ion O 2 Ϫ and the abstraction of H Ϫ from phenylsilane.

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“…For the quantitative analysis, potassium superoxide was dissolved in dimethyl sulfoxide (DMSO) containing 0.3 M 1,4,7,10,13,16-hexaoxacyclooctadecane (or 18-crown-6) according to the reported method [27], and the solution was added to 4% 2-propanol. In addition, the reactivity of hydrogen peroxide with 2-propanol was also measured.…”

Section: Blank Tests In the Darkmentioning

confidence: 99%

Quantitative analysis of superoxide ion and hydrogen peroxide produced from molecular oxygen on photoirradiated TiO2 particles

Goto

Hanada

Ohno

et al. 2004

Journal of Catalysis

294

106

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KO2/crown ether: a novel catalytic system for the hydrosilation and Tishchenko reaction of aromatic aldehydes

Cited by 18 publications

References 8 publications

Homoleptic Lanthanide Amides as Homogeneous Catalysts for Alkyne Hydroamination and the Tishchenko Reaction

Homoleptic Lanthanide Amides as Homogeneous Catalysts for Alkyne Hydroamination and the Tishchenko Reaction

Photoactivated formation of hydrogen spin adduct from phenylsilane. A new example of inverted spin trapping?

Quantitative analysis of superoxide ion and hydrogen peroxide produced from molecular oxygen on photoirradiated TiO2 particles

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