A highly diastereoselective P-Michael
addition of chiral aminophosphinic
acids to achiral acrylates has been developed, leading to phosphinic
dipeptide isosteres in high yields and dr of up to >50:1. The method
allows for the diastereoselective preparation of target compounds
without the need for chiral auxiliaries or P-chiral substrates. A
possible mechanistic explanation involves a domino chirality transfer
from the aminophosphinic acid to the P center, amplified by a crucial
benzhydryl ester group, and then to the α-carbon.