C-H Amination Catalysis from High-Spin Ferrous Complexes
Author
Metadata
Show full item recordCitation
Hennessy, Elisabeth Therese. 2013. C-H Amination Catalysis from High-Spin Ferrous Complexes. Doctoral dissertation, Harvard University.Abstract
The C-H amination and olefin aziridination chemistry of iron supported by dipyrromethene ligands (RLAr, L=1,9-R2-5-aryldipyrromethene, R = Mes, 2,4,6-Ph3C6H2, tBu, Ad, 10-camphoryl, Ar = Mes, 2,4,6-Cl3C6H2) was explored. The weak-field, pyrrole-based dipyrrinato ligand was designed to generate an electrophilic, high-spin metal center capable of accessing high valent reactive intermediates in the presence of organic azides. Isolation of the reactive intermediate in combination with a series of mechanistic experiments suggest the N-group transfer chemistry proceeds through a rapid, single-electron pathway and maintains an overall S=2 electronic configuration throughout the catalytic cycle. We have established the catalysts' strong preference for allylic amination over aziridination with olefin containing substrates. Aziridination is limited to styrenyl substrates without allylic C-H bonds, while allylic amination has been demonstrated with both cyclic and linear aliphatic alkenes. Notably, the functionalization of &alpha-olefins to linear allylic amines occurs with outstanding regioselectivity.Terms of Use
This article is made available under the terms and conditions applicable to Other Posted Material, as set forth at http://nrs.harvard.edu/urn-3:HUL.InstRepos:dash.current.terms-of-use#LAACitable link to this page
http://nrs.harvard.edu/urn-3:HUL.InstRepos:11169787
Collections
- FAS Theses and Dissertations [6138]
Contact administrator regarding this item (to report mistakes or request changes)