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Article
A Stable β-Silyl Carbocation
Journal of the American Chemical Society (1996)
  • Joseph B. Lambert, Northwestern University
  • Yan Zhao, Northwestern University
Abstract

The β effect of silicon, whereby a carbon-silicon bond substantially stabilizes an adjacent carbocation (Si-C-C+), has been widely studied mechanistically and exploited synthetically. 1-25 The phenomenon normally is invoked in reactive intermediates. Attempts to prepare stable Me3SiCH2CPh2 + under standard magic acid conditions led to loss of trimethylsilyl and observation only of CH3CPh2 +.11 A 2-(trimethylsilyl)allyl cation stable only at -100 °C did not comprise a β-effect system, as the silyl group destabilized the ion and the C-Si bond was orthogonal to the carbocation ð orbitals.21 Siehl and Kaufmann23 prepared 1-arylvinyl cations stabilized by β-silyl groups in magic acid at -120 °C. Persistent saturated β-silyl carbocations (by which we mean R3SiCH2- +C XY rather than R3SiCHd +C X), however, have never been observed by NMR, and the known unsaturated (vinylic23 and allylic21) examples are not stable in magic acid above about -100 °C. We report herein the preparation of a saturated β-silyl carbocation that is stable at room temperature.

Disciplines
Publication Date
August, 1996
Publisher Statement
Reprinted (adapted) with permission from Journal of the American Chemical Society 118 (1996): 7867, doi:10.1021/ja9613670. Copyright 1996 American Chemical Society.
Citation Information
Joseph B. Lambert and Yan Zhao. "A Stable β-Silyl Carbocation" Journal of the American Chemical Society Vol. 118 Iss. 33 (1996)
Available at: http://works.bepress.com/yan_zhao/46/