Lewis Acid Triggered Reactivity of a Lewis Base Stabilized Scandium-Terminal Imido Complex: C鈥揌 Bond Activation, Cycloaddition, and Dehydrofluorination

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• 作者：Jiaxiang Chu ; Xianghao Han ; Christos E. Kefalidis ; Jiliang Zhou ; Laurent Maron ; Xuebing Leng ; Yaofeng Chen
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：August 6, 2014
• 年：2014
• 卷：136
• 期：31
• 页码：10894-10897
• 全文大小：308K
• ISSN：1520-5126

文摘

A stable scandium-terminal imido complex is activated by borane to form an unsaturated terminal imido complex by removing the coordinated Lewis base, 4-(dimethylamino)pyridine, from the metal center. The ensuing terminal imido intermediate can exist as a THF adduct and/or undergo cycloaddition reaction with an internal alkyne, C鈥揌 activation of a terminal alkene, and dehydrofluorination of fluoro-substituted benzenes or alkanes at room temperature. DFT investigations further highlight the ease of C鈥揌 activation for terminal alkene and fluoroarene. They also shed light on the mechanistic aspects of these two reactions.