We report a novel class of C-2-symmetric chiral diols derived from the hydrobenzoin skeleton. The combination of these diols with SnCl4 under Yamamoto's concept of Lewis acid assisted Bronsted acidity (LBA catalysis) leads to, high levels of asymmetric induction in the allylboration of aldehydes by commercially available allylboronic acid pinacol ester la. The corresponding homoallylic alcohol products of synthetically useful aliphatic aldehydes are obtained in excellent yields with up to 98:2 er. This combined acid manifold is also efficient in catalyzing the diastereo- and enantioselective crotylboration of aldehydes, thus providing the propionate units in >95:5 dr and up to 98:2 er. The X-ray crystal structure of the optimal diol center dot SnCl4 complex, Vivol (4m)center dot SnCl4, unambiguously shows the Bronsted acidic character of this LBA catalyst and its highly dissymmetrical environment. Further controls have ruled out a possible boron trans-esterification mechanism with the chiral diol and point to LBA catalyst-derived activation of the pinacol allylic boronates 1. Due to slow dissociation of the diol center dot SnCl4 complex, a small excess of diol is required in order to suppress a competing racemic cycle catalyzed by free SnCl4.