Der Vielfalt von Phosphor‐Kohlenstoff‐Käfigverbindungen sind anscheinend kaum Grenzen gesetzt: Bei der Reaktion von tBuC P mit (η4‐1‐Methylnaphthalin)(η6‐toluol)eisen ließen sich neben bekannten Komplexen die Verbindungen 1 – 4 isolieren. 4 zeichnet sich durch eine 1,3‐Diphosphaallyl‐ und eine 2‐Phosphaallyl‐Teilstruktur aus.
The highly reactive arene iron complex [(η4-toluene)(η6-toluene)iron] allows the formation of C4-units from alkynes below room temperature. By this route butadiene-, cyclobutadiene-, and ferracyclopentadiene(arene)iron complexes are accessible. Synthesis, structure and the properties of one example each are reported. Ferracyclopentadienes are potential intermediates for the catalytic cyclotrimerization of alkynes in the coordination sphere of arene iron complexes.
expected in view of the electronic properties of the reaction partners.[51 Conjugation of the exocyclic double bond may be achieved by treatment with bases or, more quickly, under acid catalysis. The 6H-1,2-oxazines 5 are thereby obtained in good yields.Since 3 can be easily substituted at C-1 by deprotonation and subsequent reaction with electrophiles,[61 it is also possible to synthesize 1,2-oxazine derivatives containing two substituents in the 6-position. Whereas the addition of 2 to I-al kylated methoxyallenes affords only moderate yields (e.g., 309'0 yield of I-methyl-1-methoxyallene and 2a), the sterically encumbered hydroxylated allenes 6 and 7 give the functionalized heterocycles 8 and 9, respectively, with reasonable efficiency. A moderate diastereoselectivity (60 : 40) was found in the cycloaddition of 2a to 7 to give 9. The products 8 and 9 can also be transformed into the conjugated systems 5 by treatment with base. Na2C03 Me0 t Bu " + 2a Me0 R' R' = C(OH)Me2 8 , 49% 6 7 R' = CH(0H)Me.
56%(60 : 40) Me0 L R .
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