Copper-Catalyzed Enantioselective Formal Hydroamination of Oxa-and Azabicyclic Alkenes with Hydrosilanes and Hydroxylamines

A CuCl/(R,R)-Ph-BPE-catalyzed enantioselective formal hydroamination of oxa- and azabicyclic alkenes with polymethylhydrosiloxane (PMHS) and O-benzoylhydroxylamines has been developed. The efficient and stereoselective net addition of hydrogen and nitrogen atoms provides the corresponding optically active oxa- and azanorbornenyl- and -norbomanylamines in good yields and good enantiomeric ratios.