One‐Pot Sequence‐Controlled Synthesis of Oligosiloxanes. (15th March 2018) - Matsumoto, Kazuhiro
Abstract: Silicones (organopolysiloxanes) have found applications in a wide range of research areas, and their unique and valuable properties have rendered these materials virtually irreplaceable. Despite the fact that silicones have been employed industrially for more than 70 years, synthetic routes to generate silicones remain limited, and the sequence‐controlled synthesis of oligo‐ and polysiloxanes still represents a major challenge in silicone chemistry. Described here is a highly selective sequence‐controlled synthesis of linear, branched, and cyclic oligosiloxanes by simple iteration of two reactions, specifically, a B(C6 F5 )3 ‐catalyzed dehydrocarbonative cross‐coupling of alkoxysilanes with hydrosilanes and a B(C6 F5 )3 ‐catalyzed hydrosilylation of carbonyl compounds, in a single flask. The sequence of the resulting oligosiloxanes can be controlled precisely by the order of addition of the hydrosilane monomers. Abstract : Geordnetes Vorgehen : Ein iterativer Eintopfprozess aus B(C6 F5 )3 ‐katalysierter dehydrocarbonierender Kreuzkupplung von Alkoxysilanen mit Hydrosilanen und B(C6 F5 )3 ‐katalysierter Hydrosilylierung von Carbonylverbindungen ergibt lineare, verzweigte und cyclische Oligosiloxane in selektiver Weise. Die Sequenz der Oligosiloxan‐Produkte lässt sich über die Reihenfolge der Zugabe der Hydrosilan‐Monomere genau steuern.