The ultimate Lewis acid catalyst: using tris(pentafluorophenyl) borane to create bespoke siloxane architectures

The breadth of utility of a commercially available and stable strong Lewis acid catalyst, tris(pentafluorophenyl)borane, has been explored, highlighting its use towards a wide range of unique siloxane products and their corresponding applications. This article focuses on the variety of different outcomes that this impressive borane offers in controlled and selective manners by the variation of reaction conditions, precursor functionalities, reagent or catalyst loading, and the mechanistic considerations that contribute. With a predominant focus on the Piers-Rubinsztajn reaction and its modifications, tris(pentaflurophenyl)borane's utility is highlighted in the synthesis of linear, cyclic and macrocyclic siloxanes, aryl-/alkoxysiloxanes, and other bespoke products. The significance of the catalytic transformation within the field of siloxane chemistry is discussed alongside some of the challenges that arise from using the borane catalyst. Boranes are effective catalysts for bespoke siloxane synthesis via (modified) Piers-Rubinsztajn reactions, enabling complex macromolecular architectures with novel functionality, through careful selection of reaction components and conditions.