Catalytic Trimerization of Bis-silylated Diazomethane

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• 作者：Muhammad Farooq Ibad ; Peter Langer ; Fabian Rei脽 ; Axel Schulz ; Alexander Villinger
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：October 24, 2012
• 年：2012
• 卷：134
• 期：42
• 页码：17757-17768
• 全文大小：550K
• 年卷期：v.134,no.42(October 24, 2012)
• ISSN：1520-5126

文摘

(Me₃Si)₂CNN isomerizes upon addition of traces of [Me₃Si]p>+p> ions to give (Me₃Si)₂NNC, which then undergoes an unusual trimerization reaction to give exclusively 4-diazenyl-3-hydrazinylpyrazole. As catalyst the isonitrilium ion, [(Me₃Si)₂NNC(SiMe₃)]p>+p>, was identified and fully characterized. Experiments and computations indicate a three-step reaction including isomerization of diazomethane, a C鈥揅 or N鈥揅 coupling, and a formal cycloaddition reaction. The kinetics and thermodynamics are discussed on the basis of DFT calculations.