Electrophilic Silylation

Reactions

Various siletanes have been used as substrates for the oxidation of carbon-silicon bonds upon exposure to aqueous fluoride and peroxide. These tetraalkylsilanes offer a combination of stability and reactivity with many practical benefits, including compatibility with silicon protecting groups and electron-rich aromatic rings.
J. D. Sunderhaus, H. Lam, G. B. Dudley, Org. Lett., 2003, 8, 4571-4573.

By treatment with s-BuLi/TMEDA at -78°C, unprotected 2-methoxybenzoic acid is deprotonated exclusively in the position ortho to the carboxylate. A reversal of regioselectivity is observed when the acid is treated with n-BuLi/t-BuOK.
T.-H. Nguyen, A.-S. Castanet, J. Mortier, Org. Lett., 2006, 8, 765-768.

Various alkynylsilanes were efficiently prepared via zinc halides-mediated direct silylation of terminal alkynes with aminosilanes. Base- and nucleophile-sensitive functionalities were tolerated under the reaction conditions. The electrophilic character of this transformation is supported by initial mechanistic studies.
A. A. Andreev, V. V. Konshin, N. V. Komarov, M. Rubin, C. Brouwer, V. Gevorgyan, Org. Lett., 2004, 6, 421-424.

Hippadine and pratosine - members of the pyrrolophenanthridone alkaloid family - were synthesized.
C. G. Hartung, A. Fecher, B. Chapell, V. Snieckus, Org. Lett., 2003, 5, 1899-1902.