Outer-Sphere Electrophilic Fluorination of Organometallic Complexes

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• 作者：Lucy M. Milner ; Natalie E. Pridmore ; Adrian C. Whitwood ; Jason M. Lynam ; John M. Slattery
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：August 26, 2015
• 年：2015
• 卷：137
• 期：33
• 页码：10753-10759
• 全文大小：408K
• ISSN：1520-5126

文摘

Organofluorine chemistry plays a key role in materials science, pharmaceuticals, agrochemicals, and medical imaging. However, the formation of new carbon鈥揻luorine bonds with controlled regiochemistry and functional group tolerance is synthetically challenging. The use of metal complexes to promote fluorination reactions is of great current interest, but even state-of-the-art approaches are limited in their substrate scope, often require activated substrates, or do not allow access to desirable functionality, such as alkenyl C(sp²)鈥揊 or chiral C(sp³)鈥揊 centers. Here, we report the formation of new alkenyl and alkyl C鈥揊 bonds in the coordination sphere of ruthenium via an unprecedented outer-sphere electrophilic fluorination mechanism. The organometallic species involved are derived from nonactivated substrates (pyridine and terminal alkynes), and C鈥揊 bond formation occurs with full regio- and diastereoselectivity. The fluorinated ligands that are formed are retained at the metal, which allows subsequent metal-mediated reactivity.