Transition metal mediated isomerisation of allylic alkoxides is presented a
s a new method for enolate anion generation. The scope and limitations of e
nolate formation with the catalysts [Rh(dppe)(THF)(2)]+ClO4- and (Ph3P)(3)R
hCl are explored and the synthetic potential of the methodology demonstrate
d in the stereoselective formation and reactions of certain ketone and alde
hyde enolates.