Application of the Sharpless AD protocol to a series of alpha-(E)-benzylidene-delta-lactam precursors followed by selective deoxygenation provided efficient synthetic routes to the chiral quaternary alpha-hydroxy-gammalactam derivatives 4 and 5. These functionalized intermediates and the diol precursors 3 are regarded as novel types of D-Phe-Pro dipeptide surrogates that are useful as enzyme active site probes.