The dibenzo[b,f][1,4]oxazepine scaffold is a privileged structure in medicinal chemistry that displays a wide variety of biological and pharmacological activities. However, catalytic asymmetric methodologies for the synthesis of chiral dibenzo[b,f][1,4]oxazepine derivatives are scarce in the literature. This microreview presents an overview of enantioselective reactions in which these cyclic seven‐membered imines are used as electrophiles, including their substrate scope, limitations and application to the synthesis of related compounds.

A catalytic enantioselective aza-Reformatsky reaction with cyclic dibenzo[b,f][1,4]oxazepines and ethyl iodoacetate is reported.

(R)-VAPOL-Zn(II) complexes catalysed the enantioselective addition of terminal alkynes to cyclic benzoxathiazine 2,2-dioxides, providing the corresponding chiral propargylic sulfamidates with high yields (up to 93%) and good enantiomeric excesses (up to 87%).

An easily accessible prolinol derived ligand, (S)bis(3,5-bis(trifluoromethyl)phenyl)(pyrrolidin-2yl)methanol, has been efficiently applied in the catalytic enantioselective addition of terminal alkynes to cyclic imines using dimethylzinc (Me 2 Zn) under mild reaction conditions. The developed catalytic system led to chiral propargylic sulfamidates with high yields (up to 97%) and excellent enantioselectivities (up to 97% ee).