Attacking olefins with chiral acids: A little acid can accelerate a wide range of chemical reactions. The advent of chiral phosphoric acid derivatives has been useful for biasing these reactions toward just one of two mirror-image products. For the most part, though, these chiral catalysts have interacted with basic sites such as carbonyl groups. Tsuji et al. now extend asymmetric acid catalysis to simple carbon-carbon double bonds. Their custom imidodiphosphate forms a pocket that orients olefins to achieve mainly intramolecular alkoxylation on just one face after protonation. Science , this issue p. 1501