A New Polynitrogen‐Heterocyclic Scaffold 2,4,6,8‐Tetraazanoradamantane Skeleton: Synthesis and Conversion of Its Functionalities

Comprehensive Summary 2,4,6,8‐Tetraazanoradamantane skeleton is a unique rigid cage‐like organic structure that has not been established. In this article, a facile protocol to build all‐bridge‐position‐functionalized 2,4,6,8‐tetraazanoradamantane skeleton by condensation of glyoxal, primary amines and disubstituted malondialdehydes, which were in situ generated from 2,2‐dipropenyl‐1,3‐dioxolane or 4,4‐dimethoxyhepta‐2,5‐diene via ozonation, is reported for the first time. A variety of primary amines are compatible with this process, and the corresponding 2,4,6,8‐tetraalkyl‐2,4,6,8‐tetraazanoradamantane‐9‐one ethylene or methyl ketals were achieved in 16%—58% yields. N ‐Benzyl group could be converted to other functionalities such as acetyl and nitro, which indicates the structural diversity of this scaffold.