Ionic and Neutral Mechanisms for C-H Bond Silylation of Aromatic Heterocycles Catalyzed by Potassium tert-Butoxide. Journal of the American Chemical Society Banerjee, S., Yang, Y., Jenkins, I. D., Liang, Y., Toutov, A. A., Liu, W., Schuman, D. P., Grubbs, R. H., Stoltz, B. M., Krenske, E. H., Houk, K. N., Zare, R. N. 2017; 139 (20): 6880-6887


Exploiting C-H bond activation is difficult, although some success has been achieved using precious metal catalysts. Recently, it was reported that C-H bonds in aromatic heterocycles were converted to C-Si bonds by reaction with hydrosilanes under the catalytic action of potassium tert-butoxide alone. The use of Earth-abundant potassium cation as a catalyst for C-H bond functionalization seems to be without precedent, and no mechanism for the process was established. Using ambient ionization mass spectrometry, we are able to identify crucial ionic intermediates present during the C-H silylation reaction. We propose a plausible catalytic cycle, which involves a pentacoordinate silicon intermediate consisting of silane reagent, substrate, and the tert-butoxide catalyst. Heterolysis of the Si-H bond, deprotonation of the heteroarene, addition of the heteroarene carbanion to the silyl ether, and dissociation of tert-butoxide from silicon lead to the silylated heteroarene product. The steps of the silylation mechanism may follow either an ionic route involving K(+) and (t)BuO(-) ions or a neutral heterolytic route involving the [KO(t)Bu]4 tetramer. Both mechanisms are consistent with the ionic intermediates detected experimentally. We also present reasons why KO(t)Bu is an active catalyst whereas sodium tert-butoxide and lithium tert-butoxide are not, and we explain the relative reactivities of different (hetero)arenes in the silylation reaction. The unique role of KO(t)Bu is traced, in part, to the stabilization of crucial intermediates through cation-p interactions.

View details for DOI 10.1021/jacs.6b13032

View details for PubMedID 28462580