Mechanistic and Inducible Chirality Investigation of a Copper Mediated Allylic Amination Reaction
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Authors
Marshall, Jonathan L.
Issue Date
2005
Type
Thesis
Language
Keywords
Alternative Title
Abstract
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.
Description
44 p.
Citation
Publisher
Kalamazoo College
License
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