Mechanistic and Inducible Chirality Investigation of a Copper Mediated Allylic Amination Reaction
Marshall, Jonathan L.
MetadataShow full item record
The development of allylamines through mild reaction conditions utilizing cheap reagents is of interest in industry and medicinal chemistry. The use of C-H activation has shown much promise in this area. This study reports on the allylic amination of cyclohexene using a copper (II) catalyst. A mechanistic study with 3,3,6,6-tetradeuterocyclohexene on the allylic amination of cyclohexene with 5- phenyl-lH-tetrazole show the mechanism by which this copper (II) catalyzed reaction occurs is a 1,3-allylic rearrangement mechanism. These studies also show that the copper intermediate isomerizes on the cyclohexene resulting in 60% retention of the cyclohexene double bond and 40% migration of the cyclohexene double bond. Previous work, in addition to studies done in this laboratory, indicates that a suitable nitrogen donor to the allylic amination of cyclohexene must contain an acidic N-H bond as well as an adjacent pi-bond. When L-Proline is used as a ligand in the allylic amination of cyclohexene, a product with significant optical activity results. It is proposed that the percent enantiomeric excess is directly correlated to the extent to which the copper intermediate isomerizes on the cyclohexene.