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Governing higher-order stereogenicity is a long-standing goal in stereoselective catalysis, because it allows to achieve selectivity for more than a twofold number of stereoisomers per stereogenic unit. Current methods warrant control over the power of two stereoisomers and the configurations are routinely assigned using the descriptors ( R ) and ( S ), or related binary codes. In contrast, conformational analysis ranges beyond this dualistic treatment of stereoisomerism, which constitutes an unmet challenge for catalyst stereocontrolled processes. Herein, we now report that sixfold stereogenicity can be governed by stereoselective catalysis. By controlling a configurationally stable stereogenic axis with six large rotational barriers, a catalytic [2+2+2]-cyclotrimerization selectively governs the formation of one out of six stereoisomers with up to 0:0:2:98:0:0 stereocontrol. The underpinnings of conformational analysis and stereoselective catalysis are thereby conceptually reunited. Novel molecular architectures featuring distinct chemical topologies and unexplored chemical designs are anticipated from catalystcontrol over higher-order stereogenicities
