New and highly enantioselective catalysts for the rearrangement of meso-epoxides into chiral allylic alcohols

3-aminomethyl-2-azabicyclo(2,2.1)heptanes (4a-b) have been prepared and their Li-amides used as catalysts for the rearrangement of meso-epoxides into chiral allylic alcohols. The route is efficient for both enantiomers and diamines, and the Li-amides were found to be highly efficient. The catalytic performance can be improved by DBU, through the prevention of less selective Li-amide aggregates forming.