Enantioselective Organocatalytic Domino Oxa‐Michael/Aldol/Hemiacetalization: Synthesis of Polysubstituted Furofuranes Containing Four Stereocenters

3 in 1: A triple domino reaction was developed for the preparation of the title products in a single step starting from α,β-unsaturated aldehydes and dihydroxyacetone dimer using a chiral secondary amine catalyst (see scheme, TMS=trimethylsilyl). The title reaction sequence proceeds with the generation of four stereogenic centers to deliver bicyclic compounds in good yields and excellent diastereo- and enantioselectivities.