Dynamic Kinetic Asymmetric Allylation of Hydrazines and Hydroxylamines

Significance

Due to the importance of hydrazines and hydroxylamines as biologically active compounds, the development of stereoselective methods for their preparation constitutes an important task in asymmetric synthesis. However, a limited number of general synthetic protocols have been developed thus far. The authors report the efficient preparation of chiral hydrazines and hydroxylamines via palladium-catalyzed amination of vinyl epoxide in the presence of the Trost biphosphine ligand 1. Reactions generally proceed regioselectively, furnishing the corresponding branched products with high yields and enantio-selectivities up to 97% ee. Synthetic power of this protocol has been demonstrated via a concise synthesis of (R)-piperazic acid accomplished in five steps in 41% overall yield.