Rearrangement/Fragmentation Reactions of Oligosilanes with Aluminum Chloride

Reinvestigation of the Lewis acid catalyzed rearrangement of some open-chain permethyloligosilanes with the Al(Fe)Cl₃ catalyst system exhibited several cases of additional reactivity: namely, a fragmentation/cyclization reaction. Introduction of (trimethylsilyl)methyl substituents into the oligosilane substrates strongly facilitated this reaction, yielding cyclic or bicyclic carbacyclosilanes. Investigations concerning the composition of the catalyst system indicated that the incorporation of about 0.1% FeCl₃ into the AlCl₃ lattice provided an effective catalyst.