D/H Exchange in Nitro Diastereomers

The two diastereomers of 4-nitro-1,3-diphenylpentan-1-one behave differently in deuterium for hydrogen exchange in DMSO- d 6 /D 2 O solutions using various bases as catalyst. Reaction of the erythro diastereomer gives largely the same diastereomer upon D/H exchange (retention), i.e., exchange exceeds epimerization. Pyridine and acetonitrile as solvents lead to faster epimerization than exchange. In the threo diastereomer (DMSO- d 6 solution), epimerization exceeds exchange, and the anion to some extent regains the same hydrogen originally removed by the base on the opposite face. 2-Bromo-4-nitro-1,3-diphenylbutan-1-one undergoes ring closure to the cyclopropane faster than exchange (within seconds). The cyclopropane shows faster exchange than equilibration, i.e., retention of configuration, although it is the hydrogen α to carbonyl that is involved.