Enantio- and Site-Selective Synthesis of α-Substituted Hydrazines, Pyrazolidines, and Tertiary Alcohols by Copper-Catalyzed Allylic C–N and C–O Bond Formation

A catalytic method for the enantioselective synthesis of α-tertiary hydrazines, pyrazolidines, and tertiary alcohols containing dialkyl-substituted stereocenters is disclosed. Reactions employ simple azoarene and nitrosoarene electrophiles and undergo Cu-catalyzed site- and enantioselective C-N or C-O bond formation. Utility of the approach is demonstrated through the rapid stereoselective assembly of substituted-pyrazolidine scaffolds and 1,3-diamines.