The
communication describes an enamine-based asymmetric retro-Claisen
reaction of β-diketones by primary amine catalysis. The reaction
proceeds via a sequence of stereoselective C–C formation, C–C
cleavage, and a highly stereospecific enamine protonation to afford
chiral α-alkylated ketones or macrolides with high yields and
enantioselectivities. A detailed mechanism was explored on the basis
of experimental evidence and computational studies to account for
the observed stereocontrol
