Le dimésitylnéopentylsilène, un silène stable et facile à préparer synthèse et aspects de sa réactivité

Delpon‐Lacaze, G.; Battisti, C de; Couret, C.

doi:10.1016/0022-328x(95)06036-v

Cited by 28 publications

(21 citation statements)

References 21 publications

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“…An analogous but much easier route to new members of this novel class of compounds with cumulated silicon−carbon double bonds is the intermolecular addition of organolithium compounds at sterically hindered haloalkynylsilanes followed by metal halide elimination (Scheme , b). This route is related to the addition−elimination reaction of chlorovinylsilanes first described by Jones and later widely used in the synthesis of silenes − and germenes 1 …”

Section: Introductionmentioning

confidence: 99%

Synthesis and Reactivity of Several Stable 1-Silaallenes

et al. 1997

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Three stable 1-silapropadienes 1a−c were prepared by the intermolecular addition of organolithium reagents at the carbon−carbon triple bond of fluoroalkynylsilanes 3a,b followed by LiF elimination. The structure of 1a and of the intermediate α-lithiated fluorosilane 2a were determined by X-ray diffraction. The chemical behavior of 1-silapropadienes 1a−c differs greatly depending on the substituents on the silicon atom. When two triisopropylphenyl groups were present (1a), typical addition reactions of the SiC double bond were observed. Thermolysis of 1a yielded benzosilacyclobutene 7. For the more hindered 1-silapropadienes 1b and 1c, no reaction was observed with dioxygen, benzaldehyde, 2,3-dimethylbutadiene, or trimethylchlorosilane at room temperature. However, thermolysis of 1b or treatment with excess ethanol under neutral or acidic conditions produced 8b, the product of an intramolecular insertion of the SiC double bond into an adjoining primary C−H bond of one tert-butyl group in an ortho-position of the supermesityl substituent. In the presence of EtOD and catalytic D2SO4, this reaction occurred very rapidly at −78 °C with over 95% incorporation of deuterium in the product.

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Section: Introductionmentioning

confidence: 99%

Synthesis and Reactivity of Several Stable 1-Silaallenes

et al. 1997

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“…The compound 2 can be quite logically considered as the result of the stereospecific [2+2] cycloaddition reaction to produce only one stereoisomer, although the reactions of metallenes of Group 14 elements with benzaldehyde sometimes give the inseparable mixtures of two possible stereoisomers [14], The compound 2 has a very characteristic signal at 79.7 ppm in the 13 C NMR spectrum, which is typical for the carbon atom in the disilaoxetane four-membered ring system. The compound 2 can be quite logically considered as the result of the stereospecific [2+2] cycloaddition reaction to produce only one stereoisomer, although the reactions of metallenes of Group 14 elements with benzaldehyde sometimes give the inseparable mixtures of two possible stereoisomers [14], The compound 2 has a very characteristic signal at 79.7 ppm in the 13 C NMR spectrum, which is typical for the carbon atom in the disilaoxetane four-membered ring system.…”

Section: Resultsmentioning

confidence: 99%

Foreword Interaction of 1-Disilagermirene With Carbonyl Compounds

Lee¹,

Ichinohe²,

Sekiguchi³

2002

Main Group Metal Chemistry

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“…This substrate -prepared from (dimesitylfluorosilyl)ethene and tert-butyllithiumgave the silazetidine 30e on treatment with two equivalents of tert-butyl isocyanide. 23 It might be added that azasiliridines related to 29 were obtained very recently from isocyanides and a disilene like R 2 Si=SiRPh [R = 2,4,6-(i-Pr) 3 C 6 H 2 ], but, remarkably, these products (which have a semicyclic C=Si bond instead of a C=C bond) did not undergo isocyanide insertion to give four-membered rings, i.e. silylidene analogs of 30.…”

Section: Methodsmentioning

confidence: 99%