Fragmentation of Homoallylic Alkoxides. Thermolysis of Potassium 2-Substituted Bicyclooct-5-en-2-alkoxides

Article abstract of DOI:10.1002/hlca.19810640726

Thermolysis of the potassium 2-substituted bicyclo<2.2.>oct-5-en-2-alkoxides derived from alcohols 2-17 at 90-120 deg C in hexamethylphosphoric triamide affords unsaturated ketones resulting from allylic bond cleavage.The mechanistic and synthetic aspects of this anionic fragmentation are discussed with reference to the formation of 1-(3'-cyclohexenyl)-2-alkanones 18-28 via initial heterolytic C(1),C(2)-bond cleavage in the substrate alkoxide and regioselective, intramolecular protonation of the resultant transient allylic anion.