Illuminating the multiple Lewis acidity of triaryl-boranes via atropisomeric dative adducts

Abstract

Using the principle that constrained conformational spaces can generate novel and hidden molecular properties, we challenged the commonly held perception that a single-centered Lewis acid reacting with a single-centered Lewis base always forms a single Lewis adduct. Accordingly, the emergence of single-centered but multiple Lewis acidity among sterically hindered and non-symmetric triaryl-boranes is reported. These Lewis acids feature several diastereotopic faces providing multiple binding sites at the same Lewis acid center in the interaction with Lewis bases giving rise to adducts with diastereomeric structures. We demonstrate that with a proper choice of the base, atropisomeric adduct species can be formed that interconvert via the dissociative mechanism rather than conformational isomerism. The existence of this exotic and peculiar molecular phenomenon was experimentally confirmed by the formation of atropisomeric piperidine-borane adducts using state-of-the-art NMR techniques in combination with computational methods.