ELECTRONIC CONTROL OF ENANTIOSELECTIVITY IN THE PALLADIUM-CATALYZED ASYMMETRIC ALLYLIC SUBSTITUTION OF TRANS 4-TBUTYL-1-VINYLCYCLOHEXYL BENZOATES

The enantioselectivily in the palladium-catalyzed substitution of allylic benzontes 1 by sodium dimethylmalonate was influenced by polar and steric effects of the substituents in the phenyl ring of the benzoate. Electron-donating p-substituents afforded effective chiral differentiation (up to 90%ee). Electron-withdrawing substituents, t-butyl-p-substituent, N,N-dialkylamino p-substituents or o-substituents were detrimental to steric differentiation (down to 22%ee). Di- and tri-methoxy substituted benzoates gave moderate asymmetric inductions (46-70 %ee).