Cavity-arbitrated enantioinduction by calix[4]arene-annexed BINOL catalysts for cyanosilylation of aldehydes.

We report a cavity-controlled catalytic strategy for the highly enantioselective cyanosilylation of aldehydes using a BINOL-functionalized calix[4]arene catalyst. The catalyst combines a chiral BINOL-derived active site with a well-defined supramolecular cavity, enabling cooperative substrate binding and asymmetric induction. Systematic catalyst design revealed a strong dependence of enantioselectivity on cavity dimensions, highlighting the crucial role of geometric confinement in stereocontrol.