Selective [3+1] Fragmentations of P₄ by “P” Transfer from a Lewis Acid Stabilized [RP₄]⁻ Butterfly Anion

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• 作者：Jaap E. Borger ; Dr. Andreas W. Ehlers ; Dr. Martin Lutz ; Dr. J. Chris Slootweg and Prof. Dr. Koop Lammertsma
• 刊名：Angewandte Chemie
• 出版年：2017
• 出版时间：January 2, 2017
• 年：2017
• 卷：129
• 期：1
• 页码：291-296
• 全文大小：1134K
• ISSN：1521-3757

文摘

Two [3+1] fragmentations of the Lewis acid stabilized bicyclo[1.1.0]tetraphosphabutanide Li[Mes*P₄⋅ BPh₃] (Mes*=2,4,6-tBu₃C₆H₂) are reported. The reactions proceed by extrusion of a P₁ fragment, induced by either an imidazolium salt or phenylisocyanate, with release of the transient triphosphirene Mes*P₃, which was isolated as a dimer and trapped by 1,3-cyclohexadiene as a Diels–Alder adduct. DFT quantum chemical computations were used to delineate the reaction mechanisms. These unprecedented pathways grant access to both P₁- and P₃-containing organophosphorus compounds in two simple steps from white phosphorus.