Peterson olefination

The Peterson olefination (also called the Peterson reaction) is the chemical reaction of α-silyl carbanions (1 in diagram below) with ketones (or aldehydes) to form a β-hydroxysilane (2) which eliminates to form alkenes (3). Several reviews have been published. One attractive feature of the Peterson olefination is that it can be used to prepare either cis- or trans-alkenes from the same β-hydroxysilane. Treatment of the β-hydroxysilane with acid will yield one alkene, while treatment of the same β-hydroxysilane with base will yield the alkene of opposite stereochemistry. The action of base upon a β-hydroxysilane (1) results in a concerted syn elimination of (2) or (3) to form the desired alkene. The penta-coordinate silicate intermediate (3) is postulated, but no proof exists to date. Potassium alkoxides eliminate quickly, while sodium alkoxides generally require heating. Magnesium alkoxides only eliminate in extreme conditions. The order of reactivity of alkoxides, K > Na >> Mg, is consistent with higher electron density on oxygen, hence increasing the alkoxide nucleophilicity. The treatment of the β-hydroxysilane (1) with acid results in protonation and an anti elimination to form the desired alkene. When the α-silyl carbanion contains only alkyl, hydrogen, or electron-donating substituents, the stereochemical outcome of the Peterson olefination can be controlled, because at low temperature the elimination is slow and the intermediate β-hydroxysilane can be isolated. Once isolated, the diastereomeric β-hydroxysilanes are separated. One diastereomer is treated with acid, while the other is treated with base, thus converted the material to an alkene with the required stereochemistry. When the α-silyl carbanion contains electron-withdrawing substituents, the Peterson olefination directly forms the alkene. The intermediate β-hydroxysilane cannot be isolated as it eliminates in-situ. The basic elimination pathway has been postulated in these cases. Acidic elimination conditions are sometimes not feasible as the acid also promotes double bond isomerization.