The work presented herein describes the synthesis of a formerly inaccessible class of heterocyclic compounds. The reaction relies on α‐phthalimido‐amides, which are readily prepared from amino acids in 2 simple reactions steps. Under amide activation conditions in which classical keteniminium ions are not formed, the nitrile solvent is incorporated into the new fused 7‐membered ring system. Due to the absence of a keteniminium intermediate, the stereogenic information in the α‐position is fully retained.

The Cover Feature shows the reaction of an amino acid derivative with acetonitrile to form a formally unknown heterocyclic compound. The reaction is mediated by trifluoro‐methanesulfonic anhydride, which unlashes this unconventional reactivity and is illustrated by the scissors, which cut the rope holding the weight of CH3CN. The background shows a 3D model of the product, which is based on the X‐ray diffraction analysis of its single crystal. More information can be found in the Communication by N. Maulide et al.