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

Abstract

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.