Silanediyl 2 (generated by thermolysis of cyclotrisilane 1) reacts with benzophenone, tetracyclone, and fluorenone to yield products, which may originate from highly reactive siloxiranes as intermediates. However, using adamantanone as ketone, stable siloxirane 24 is obtained. The interaction of 2 with benzophenone anil or 36 gives heterocyclic compounds 31 and 37, respectively. The involvement of silaziridines in these reactions, as well as in the reactions of 1 with 1,4-diaza-1,3-butadienes 41a and b, which yield the expected formal [4 + 1] cycloaddition products, remains questionable.
The reaction of 1,1‐dibromo‐2,2‐bis(chloromethyl)cyclopropane (2) with methyllithium in ether led to a solution of [1.1.1]‐propellane (1) in a yield of 70%. 1 could also be prepared free of solvent by reaction of 2 with lithium powder in triglyme/n‐decane at 73°C.
In der „klassischen”︁ Cyclopropanierung von Bicyclo[1.1.0]butan‐Derivaten und in der Carbenoid‐Cyclisierung von 1‐Lithio‐1‐halo‐3‐alkylidencyclobutanen, bei denen der Vierring Teil eines Bicyclo[3.1.1]heptan‐ oder Bicyclo[2.1.1]hexan‐Systems ist, wurden zwei effiziente Wege zu [1.1.1]Propellanen gefunden. Von zwei Modellen, 61 und 45, wurden die Röntgenstrukturen ermittelt.
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