ORGN 120 |
| The SN2 reaction is a commonly used reaction in organic chemistry. Frontier molecular orbital theory can falsely lead one to believe that its electrophilic equivalent, the SE2 reaction, can not exist. Despite this, details of Hartree-Fock calculations, using the 6-31G** basis set, will be presented indicating that the SE2 reaction of tertiary-butyl cation with tetramethylsilane to give neopentane and trimethylsilyl cation follows a single-step inversion mechanism, is exothermic, and proceeds with a low enough energy of activation to be useful. Practical alkylations of carbon cations with tetramethylsilane and tetraethylsilane have been accomplished in good yield and will be reported. For example, carboxylic acids can be converted in one pot to methyl or ethyl ketones in two steps; a catalytic Vilsmeier conversion to the acid chloride followed by alkylation of the intermediate acid chloride with a tetraalkylsilane using aluminum chloride. |
|
Asymmetric Reactions and Syntheses, Physical Organic Chemistry, Combinatorial Chemistry, Total Synthesis
8:00 PM-10:00 PM, Sunday, 26 March 2006 Georgia World Congress Center -- Ex. Hall B4, Poster
Division of Organic Chemistry |