Chiral oxazolidinones were previously thought to control cycloaddition stereoselectivity by steric crowding of one face of the substrate. We have discovered that in 4+3 cycloaddition reactions of oxallyls, the stereoinduction is caused instead by stabilising CH-π interactions that lead to reaction at the more crowded face of the oxazolidinone. Density functional theory calculations on the 4+3 cycloadditions of oxazolidinone-substituted oxyallyls with furans establish unexpected transition state conformations and a new explanation of selectivity.