Ultrafast Click Chemistry with Fluorosydnones

详细信息    查看全文

• 作者：Dr. Hui Liu ; Dr. Davide Audisio ; Lucie Plougastel ; Elodie Decuypere ; David-Alexandre Buisson ; Dr. Oleksandr Koniev ; Dr. Sergii Kolodych ; Dr. Alain Wagner ; Dr. Mourad Elhabiri ; Anna Krzyczmonik ; Dr. Sarita Forsback ; Prof. Olof Solin ; Prof. Vé ; ronique Gouverneur and Dr. Fré ; dé ; ric Taran
• 刊名：Angewandte Chemie International Edition
• 出版年：2016
• 出版时间：September 19, 2016
• 年：2016
• 卷：55
• 期：39
• 页码：12073-12077
• 全文大小：1765K
• ISSN：1521-3773

文摘

We report the synthesis and reactivity of 4-fluorosydnones, a unique class of mesoionic dipoles displaying exquisite reactivity towards both copper-catalyzed and strain-promoted cycloaddition reactions with alkynes. Synthetic access to these new mesoionic compounds was granted by electrophilic fluorination of σ-sydnone Pd^II precursors in the presence of Selectfluor. Their reactions with terminal and cyclic alkynes were found to proceed very rapidly and selectively, affording 5-fluoro-1,4-pyrazoles with bimolecular rate constants up to 10⁴ m⁻¹ s⁻¹, surpassing those documented in the literature with cycloalkynes. Kinetic studies were carried out to unravel the mechanism of the reaction, and the value of 4-fluorosydnones was further highlighted by successful radiolabeling with [¹⁸F]Selectfluor.