REDUCTIVE COUPLING OF α,β UNSATURATED KETONES III (+)-PULEGONE: AN EXAMPLE OF UMPOLUNG

Article abstract of DOI:10.1016/S0040-4039(00)84934-5

Treatment of (+)-pulegone with TiCl4-Mg/THF complex unexpectedly yields a) menthone (when the reaction is carried out with t-butyl alcohol), b) allylmenthadienes (when it is carried out with allylic halides), c) ketol dimers (when no additive electrophilic species is used); a bielectronic transfer mechanism, leading to an umpolung on (+)-pulegone is proposed an explanation for the formation and the structure of the products.