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

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.

Expanding the Boundaries of Water-Tolerant Frustrated Lewis Pair Hydrogenation: Enhanced Back Strain in the Lewis Acid Enables the Reductive Amination of Carbonyls.

The development of a boron/nitrogen-centered frustrated Lewis pair (FLP) with remarkably high water tolerance is presented. As systematic steric tuning of the boron-based Lewis acid (LA) component revealed, the enhanced back-strain makes water binding increasingly reversible in the presence of relatively strong base. This advance allows the limits of FLP's hydrogenation to be expanded, as demonstrated by the FLP reductive amination of carbonyls. This metal-free catalytic variant displays a notably broad chemoselectivity and generality.