The incorporation of a trifluoromethyl (TFM) group into various organic molecules has been shown to have interesting effects with regards to their chemical and physical properties. This poster presentation will highlight two projects: (1) TFM carbinols can be oxidized to trifluoromethyl ketones using an oxoammonium salt, 4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate. This powerful reaction has been probed by computational techniques (B3LYP/6-31+g(d)) to obtain critical thermodynamic data. This has been correlated with experimental data to determine the mechanistic pathway for the reaction.  (2) Computational methods have also been used to investigate the interaction between various silyl moieties and destabilized TFM carbenium ions.  The stabilizing features and mechanistic details of TFM cyclopropane and cyclobutane formation via ?-silyl and d-silyl effects, respectively, have been investigated. The computational data serves to shed light upon these unique systems and has been shown to greatly complement experimental results.

Theoretical studies elucidating mechanistic details of the oxidation of trifluoromethyl carbinols and cyclization reactions of strained trifluoromethyl-containing molecules

244th National Meeting (2012)

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