Reactivite nucleophile des cyclanones: influence de la stereochimie cis/trans en serie bicyclique

Article abstract of DOI:10.1139/v82-336

The relative reactivities of a number of cis/trans pairs of bicyclic ketones in the 1- and 2-decalone series (2-decalone; 10-methyl-2-decalone; 9-methyl-1-decalone; and 3,10-dimethyl-2-decalone) have been studied for the nucleophilic addition of hydroxylamine in acidic medium.The results obtained as well as the rate constants for neutral or acid catalysed addition always reveal a slight preference for the trans-isomer (x 2.4).This result agrees with the proposal that preferential equatorial attack of a nucleophile is caused by conformational factors related to a steroid <*> non-steroid conformation equilibrium in the cis-isomers.