Dibromohydantoins as halogen bond (XB) donors: a route toward the introduction of chirality in halogen bonded systems

N,N'-Dibromohydantoins, known as electrophilic bromination reagents, are successfully used here as halogen bond (XB) donors, as demonstrated in their crystalline adducts with para-substituted pyridines acting as halogen bond acceptors. 1 : 1 adducts of the achiral 5,5-dimethyl- N, N'-dibromohydantoin (DBH) are crystallized with methylisonicotinate, 4- trifluoromethylpyridine and 4- cyanopyridine, while both nitrogen atoms of pyrazine are engaged in halogen bonding in the 2 : 1 adduct (DBH)(2).(pyrazine). A strengthening of the XB interaction between the imidic N-Br group of DBH and the pyridinic nitrogen atom is observed with the more electron rich pyridines in the order Py-CO2Me > Py-CF3 > Py-CN > pyrazine. Chiral hydantoins and their N, N'-dibromo derivatives are obtained in good yields from different amino acids (phenylglycine, phenylalanine, valine and leucine). The ability of such enantiopure N-iodoimide derivatives to act as halogen-bond donors is demonstrated in the 1 : 1 methylisonicotinate adduct with (S)-5-isobutyl-N, N'-dibromohydantoin.