A low-temperature (-95 degrees C) protocol for intermolecular cycloadditions of furan to chiral silyloxyallyl cations in dichloromethane is described. Key precursors are open-chain, mixed a-ketoacetals, which are chiral. The resulting [4+3] cycloadducts are densely functionalized and are isolated as single enantiomers in high chemical yield. The yield of the cycloadducts increases with increasing dilution. Three and four stereogenic centres are created in one single step.