报告题目: |
Discrete Late Metal Nitrenes in Catalytic C-H Amination |
报告人: |
Timothy H. Warren |
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Prof.
Department of Chemistry
Georgetown University
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报告时间: |
2008-06-23 15:30 |
报告地点: |
化学系新馆406会议室 |
主办单位: |
清华大学化学系 |
简介: |
Catalytic C-H amination offers the opportunity to directly convert C-H bonds into amine functionalities without the need for prior chemical modification of these normally unreactive C-H bonds. Electrophilic, late transition metal-nitrene complexes [M]=NR are believed to be the active intermediates in this challenging transformation, providing greater chemoselectivity than free nitrenes themselves. Using well-defined β-diketiminato complexes of Co, Ni, and Cu, we demonstrate the synthesis of discrete metal-nitrene complexes which enables a detailed examination of their electronic structure as well as reactivity towards a variety of substrates. These fundamental inorganic synthetic studies allow for the rational development of a catalytic system for the efficient amination of a wide variety of sp3-hybridized C-H bonds with organoazides.
Leading References:
(1) “Transient Terminal Cu-Nitrene Intermediates from Discrete Dicopper Nitrenes” Badiei, Y. M.; Krishnaswamy, A.; Melzer, M.; Warren, T. H. J. Am. Chem. Soc.2006, 128, 15056-15057.
(2) “A Terminal Ni(III)-Imide with Diverse Reactvity Pathways” Kogut, E.; Wiencko, H. L.; Zhang, L.; Cordeau, D. C.; Warren, T. H.* J. Am. Chem. Soc. 2005, 127, 11248-11249.
(3) “[Me2NN]Co(η6-toluene): O=O, O=N, and N=N Bond Cleavage Provides β- Diketiminato μ-Oxo and Imido Complexes” Dai, X.; Kapoor, P.; Warren, T. H. J. Am. Chem. Soc. 2004, 126, 4798-4799. |
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