Synthesis and reactions of [tris(trimethylsilyl)methyl]ethyl dichlorosilane

New straightforward route for the synthesis of some 1‐oxa‐2‐silacyclopentane derivatives

“…Glycidyl methacrylate (GM) random copolymers with 4-methyl-and 4-methoxy styrene, synthesized by solution free radical polymerization at 70 (±1) °C with α,α-azobis(isobutyronitrile) (AIBN) as initiator, contained pendant epoxide functions. Treatment of these with (HSiMe 2 ) 3 CLi did not lead to intramolecular nucleophilic attack as found for simple epoxides.…”

“…Silicon-substituted alkyllithium compounds, in particular (Me 3 Si) 3 CLi have been used to synthesis organic compounds containing very bulky substituents, many of which possess unique structures and display novel reactivity [1][2][3]. It is also known that [(HSiMe 2 ) 3 CLi].2THF is formed in excellent yield from the reaction of (HSiMe 2 ) 3 CH with (Me 2 CH) 2 NLi in THF [4].…”

“…It is also known that [(HSiMe 2 ) 3 CLi].2THF is formed in excellent yield from the reaction of (HSiMe 2 ) 3 CH with (Me 2 CH) 2 NLi in THF [4]. Attachment of tris(trimethylsilyl)methyl groups to macromolecular chains leads to important modifications of polymer properties such as potential membrane materials in separation processes and an increase in glass transition temperature [5][6].…”

“…These useful intermediates can be prepared by dehydrogenation [8], intramolecular hydrosilylation [9], extrusion of isocyanates [10], elimination of dibutyltin chloride from the 2-oxastannacyclopentane by reaction with dimethyldichlorosilane [11], cyclization of (ω-ethoxysilylalkoxy)trimethylsilanes [12] (Scheme 1), insertion of carbonyl groups to oxasilacyclopropane [13,14], and intramolecular bis-silylation [15] of alkenes promoted by a palladium isocyanide catalyst. Treatment of (HSiMe 2 ) 3 CLi with some simple epoxides gave 3,3-bis-(dimethylsilyl)-1-oxa-2-silacyclopentanes in an unusual but straightforward process [17]. To seek more evidence for the proposed mechanism we studied the reaction of [(HSiMe 2 ) 3 CLi].2THF with some other epoxides and polymers containing epoxy groups on the side chain.…”

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3 CLi, reacts with allyl, phenyl, benzyl, n-propyl and n-butyl glycidyl ethers in THF at -5 °C to give 1-oxa-2-silacyclopentane derivatives. It seems that ring closure is facilitated by conversion of the Si-H bond into an Si-O bond.

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