Radiolytic silylation of alkenes and alkynes by gaseous RSi ions. Stereochemical evidence for the β-silyl effect
Journal of the American Chemical Society, ISSN: 0002-7863, Vol: 120, Issue: 7, Page: 1523-1527
1998
- 23Citations
- 3Captures
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Article Description
Carbocation intermediate stabilized by a β silyl group have been characterized using the silylation of alkenes by RSi ions as a route of formation. Neutral silylated products have been obtained from the reaction of RSi ions, generated in a gaseous medium at atmospheric pressure by a radiolytic technique, with selected alkenes, alkynes, and allene, thereby indicating the occurrence of electrophilic silylation. Notable fectures of the charged silylated intermediates emerge from the isomeric product distribution. The silylation of cis- and trans-2-butene shows a high degree of retention of configuration, as expected if a bridged species (I) were the reaction intermediate. Alternatively, the intermediacy of an open structure (II), whereby C-C bond rotation is inhibited by the hyperconjugative interaction between the β silyl group and the vacant up orbital, should be inferred. The charged intermediates from the silylation of alkenes and alkynes are found to be unreactive toward conceivable isomerizations to more stable species, such as the ones bearing the positive charge of silicon. Stereoelectronic factors affect the deprotonation of the silylated intermediates, which may involves loss of the proton either the α or the γ position with respect to the silylated carbon. A comparison of the reactivity of alkenes and alkynes in the cationic silylation reaction is presented.
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