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Issue 10, 2014
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1,3-γ-Silyl-elimination in electron-deficient cationic systems

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Abstract

Placement of an electron-withdrawing trifluoromethyl group (–CF3) at a putative cationic centre enhances γ-silyl neighbouring-group participation (NGP). In stark contrast to previously studied γ-silyl-substituted systems, the preferred reaction pathway is 1,3-γ-silyl elimination, giving ring closure over solvent substitution or alkene formation. The scope of this cyclopropanation reaction is explored for numerous cyclic and acyclic examples, proving this method to be a viable approach to preparing CF3-substituted cyclopropanes and bicyclic systems, both containing quaternary centres. Rate-constants, kinetic isotope effects, and quantum mechanical calculations provided evidence for this enhancement and further elaborated the disparity in the reaction outcome between these systems and previously studied γ-silyl systems.

Graphical abstract: 1,3-γ-Silyl-elimination in electron-deficient cationic systems

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Supplementary files

Article information


Submitted
11 Jun 2014
Accepted
23 Jun 2014
First published
03 Jul 2014

Chem. Sci., 2014,5, 3983-3994
Article type
Edge Article

1,3-γ-Silyl-elimination in electron-deficient cationic systems

M. A. Mercadante, C. B. Kelly, T. A. Hamlin, K. R. Delle Chiaie, M. D. Drago, K. K. Duffy, M. T. Dumas, D. C. Fager, B. L. C. Glod, K. E. Hansen, C. R. Hill, R. M. Leising, C. L. Lynes, A. E. MacInnis, M. R. McGohey, S. A. Murray, M. C. Piquette, S. L. Roy, R. M. Smith, K. R. Sullivan, B. H. Truong, K. M. Vailonis, V. Gorbatyuk, N. E. Leadbeater and L. J. Tilley, Chem. Sci., 2014, 5, 3983
DOI: 10.1039/C4SC01732C

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