Ion-cyclotron resonance studies of the reactions between ethers and the trimethylsilyl cation
- 1 January 1979
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Perkin Transactions 2
- No. 12,p. 1640-1643
- https://doi.org/10.1039/p29790001640
Abstract
Nucleophilic attack of a dialkyl ether (R–O–R′) at the electrophilic silicon centre of the trimethylsilyl cation (Me3Si+) produces the 1 : 1 adduct Me3Si–ORR′. The adduct generally decomposes by elimination of a neutral fragment. When R > Me, the adduct undergoes characteristic elimination of the olefin (R–H·). When R′ > R, the adduct eliminates the larger olefin preferentially. This elimination proceeds by β-hydrogen transfer to oxygen through a four-membered transition state, with the hydrogen transfer being involved in the rate-determining step. When R = Me and R′= CH2CH2F, an entirely different decomposition channel is noted, i.e. Me3SiF is eliminated. The adducts from cyclic ethers generally fragment to Me3Si–OCH2, except for adducts derived from ethylene oxide derivatives, which do not decompose.Keywords
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