Condensing the Cage: Novel Insights Into the Reaction Pathway of Isowurtzitane Cage Formation

ABSTRACT In this contribution, we propose an alternative reaction pathway for the formation of isowurtzitane cages. These cage products are the basis for the synthesis of CL‐20, a highly prized energetic material and propellant. Isowurtzitane cages are typically formed under acid‐catalysed conditions via the condensation reaction between glyoxal and certain amines. Here, we report the cage formation proceeds via a series of addition reactions from the previously established diimine intermediate. This reaction pathway has been investigated in detail with HRMS and NMR, as well as isolation of key intermediates providing a comprehensive alternative pathway for the cage formation.