1,4,6,10-Tetraazaadamantanes (TAADs) with N-amino groups: synthesis and formation of boron chelates and host-guest complexes

Artem N Semakin; Ivan S Golovanov; Yulia V Nelyubina; Alexey Yu Sukhorukov

doi:10.3762/bjoc.18.148

1,4,6,10-Tetraazaadamantanes (TAADs) with N-amino groups: synthesis and formation of boron chelates and host-guest complexes

Beilstein J Org Chem. 2022 Oct 11:18:1424-1434. doi: 10.3762/bjoc.18.148. eCollection 2022.

Authors

Artem N Semakin¹, Ivan S Golovanov¹, Yulia V Nelyubina², Alexey Yu Sukhorukov¹

Affiliations

¹ Laboratory of organic and metal-organic nitrogen-oxygen systems, N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect, 47, Moscow, 119991, Russian Federation.
² Center for molecular composition studies, A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 119991, Vavilova str. 28, Moscow, Russian Federation.

Abstract

A synthetic route to 1,4,6,10-tetraazaadamantanes (TAADs) bearing free and protected amino groups at the bridge N-atoms has been developed via intramolecular cyclotrimerization of C=N units in the corresponding tris(hydrazonoalkyl)amines. In a similar fashion, unsymmetrically substituted TAADs having both amino and hydroxy groups at the bridge N-atoms were prepared via a hitherto unknown co-trimerization of oxime and hydrazone groups. The use of N-TAAD derivatives as potential ligands and receptors was showcased through forming boron chelates and host-guest complexes with water and simple alcohols.

Keywords: azaadamantanes; cyclotrimerization; hydrazones; inclusion complexes; molecular recognition.

Grants and funding

This work was supported by the Russian Foundation for Basic Research (grant 20-03-00510_a). X-ray diffraction data for Bn-4c(bromide)·3CD₃OD, 19e·3HCl·H₂O, and 21·2D₂O were collected with financial support from the Ministry of Science and Higher Education of the Russian Federation using the equipment of the Center for molecular composition studies of INEOS RAS.