title: Substituted diazatetracyclo[4.4.0.1(3,10).1(5,8)]dodecanes as stable caged proton sponges.
abstract: Herein, we report a molecular framework design differing significantly from the traditional topology of proton sponges. We developed a synthetic approach to the preparation of caged secondary amines by acid-catalyzed rearrangement of fused tetracyclic heterocycles synthesized by intramolecular criss-cross cycloaddition. Alkylation of amines led to air nonsensitive diazatetracyclo[4.4.0.1(3,10).1(5,8)]dodecanes (DTDs) with rare alicyclic scaffolding in high overall yields. Their pK(BH)+ values were determined by transprotonation experiments as well as their sensitivity toward nucleophiles, acids and bases. Crystal structures of free base and monoprotonated form are discussed.
authors.affiliation: Department of Chemistry, Faculty of Science, Masaryk University, Kotlářská 2, 611 37 Brno, Czech Republic.
authors.forename: Juraj
authors.initials: J
authors.lastname: Galeta
authors.forename: Milan
authors.initials: M
authors.lastname: Potáček