Abstract
An unprecedented reactivity has been introduced to 3-isopropyl-1,4-benzodiazepine-2,5-dione thanks to N-Boc activation. Under basic conditions, a transannular rearrangement occurred by ring contraction to furnish a 3-aminoquinoline-2,4-dione with good to excellent enantiomeric purity. Depending on the nature of the base, either enantiomer can be obtained in a stereocontrolled manner. This enantiodivergent synthesis could be assigned to the conformational equilibrium of the starting material, which was studied with the help of DFT calculations.