Synthesis of Octachloro- and Octaazido-Functionalized T-Cages and Application to Recyclable Palladium Catalyst.

Unprecedented T-cages bearing eight chloromethyldimethylsilylethyl substituents were obtained in excellent yield from the readily and commercially available octavinylsilsesquioxane. The chloro groups can be quantitatively substituted by azido ones to yield the corresponding octaazido T without rearrangement of the cage. The syntheses of both functionalizable POSSs are scalable (gram-scale).

Synthesis of Tetrachloro, Tetraiodo, and Tetraazido Double-Decker Siloxanes.

A convenient and scalable (gram-scale) route to unprecedented TD-double-decker siloxanes (DDSQs) bearing four chloro () or four azido () groups is reported. Both compounds were characterized and proved to undergo successful nucleophilic substitution for (with iodide or azide) and copper-catalyzed azide-alkyne [3 + 2] cycloaddition for . All of these transformations occurred under mild conditions, and the corresponding DDSQs were prepared in very high yields.