Uncover the strength of polyhedral dicarbaboranes as the next generation of superbases in organocatalysis

Abstract Although boron compounds appear in many chemical transformations, it is hard to imagine, these usually Lewis acidic, species would act as Lewis bases or even base-catalysts. Here we show that the adduct o- 2 , formed by the reaction of closo −1,2-dicarbadecaborane(10) with two equivalents of an N -heterocyclic carbene, exhibits superbasic properties with proton affinity surpassing that of the parent carbene as well as commercial superbases. It reacts selectively with C-acids, solvents and water, with its reactivity strongly influenced by substrate pK A . o- 2 facilitates various Lewis base-catalyzed transformations—including aldol condensation, the Thorpe reaction, Michael addition, Robinson annulation and β-nitrostyrene polymerization—with exceptional efficiency and selectivity. Moreover, o- 2 effectively catalyzes highly diastereoselective conjugate additions of 4-substituted pyrazolones to electron-poor olefins and spirocyclizations of pyrazolones with dibenzylideneacetones. A notable tolerance of catalyst to significant amounts of water and base-sensitive functional groups has also been observed.