Angew. Chem. Int. Ed. : RESOLV member Prof. Stefan M. Huber presents the second generation of a bidentate Iodine(I)-based halogen bond donor as a modifiable and highly active chiral halogen bonding catalyst. With these modified derivatives, high stereocontrol of up to 98% ee could be achieved in a model Mukaiyama aldol reaction for a range of different substrates. Importantly, the crucial role of halogen bonding in this catalytic process was demonstrated by the low performance of the non-iodinated variants and by DFT calculations. The latter also indicate that the stereoinduction is based on the imposed orientation of the substrates towards each other.
