2,4,9‐Triazaadamantanes with “Clickable” Groups: Synthesis, Structure and Applications as Tripodal Platforms

Semakin, Artem N.; Nelyubina, Yulia V.; Ioffe, Sema L.; Sukhorukov, Alexey Yu.

doi:10.1002/ejoc.202000832

Cited by 7 publications

(5 citation statements)

References 90 publications

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“…Remarkable features of all three structures are reduced pyramidality of nitrogen atoms (deviation of nitrogen from the mean plane formed by substituents is ca. 0.4 Å) and shortening of N–O bonds compared to noncoordinated derivatives of tfoH 3 (1.42–1.47 Å − ). These features are usually an indication of hyperconjugation interactions involving a lone electron pair ( n → σ* donation, vide infra ) .…”

Section: Resultsmentioning

confidence: 95%

Revealing the Structure of Transition Metal Complexes of Formaldoxime

et al. 2021

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Aerobic reactions of iron(III), nickel(II), and manganese(II) chlorides with formaldoxime cyclotrimer (tfoH 3 ) and 1,4,7-triazacyclononane (tacn) produce indefinitely stable complexes of general formula [M(tacn)(tfo)]Cl. Although the formation of formaldoxime complexes has been known since the end of 19th century and applied in spectrophotometric determination of Dmetals (formaldoxime method), the structure of these coordination compounds remained elusive until now. According to the X-ray analysis, [M(tacn)(tfo)] + cation has a distorted adamantane-like structure with the metal ion being coordinated by three oxygen atoms of deprotonated tfoH 3 ligand. The metal has a formal +4 oxidation state, which is atypical for organic complexes of iron and nickel. Electronic structure of [M(tacn)(tfo)] + cations was studied by XPS, NMR, cyclic (CV) and differential pulse (DPV) voltammetries, Mossbauer spectroscopy, and DFT calculations. Unusual stabilization of high-valent metal ion by tfo 3− ligand was explained by the donation of electron density from the nitrogen atom to the antibonding orbital of the metal−oxygen bond via hyperconjugation as confirmed by the NBO analysis. All complexes [M(tacn)(tfo)]Cl exhibited high catalytic activity in the aerobic dehydrogenative dimerization of p-thiocresol under ambient conditions.

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Section: Resultsmentioning

confidence: 95%

Revealing the Structure of Transition Metal Complexes of Formaldoxime

et al. 2021

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“…However, this reaction is slow and reversible (upon heating adamantane structure 2 reverts to the tris-oxime form 1 ). Previous experimental and computational data evidence that cyclotrimerization of hydrazone groups proceeds more readily compared to oximes [ 18 ]. Hence, hydrazones 3 were expected to cyclize to corresponding TAADs 4 with high efficiency.…”

Section: Resultsmentioning

confidence: 99%

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

Semakin¹,

Golovanov²,

Nelyubina³

et al. 2022

Beilstein J. Org. Chem.

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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.

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“…The methods of the synthesis of azaadamantanes are considered in detail in the works [ 3 , 4 , 11 , 12 ]. In this review, for the reader’s convenience, we present the most widely used approaches to the synthesis of 1,3-diazaadamantanes and 1,3,5-triazaadamantanes, the skeletons of which are most often found in the biologically active azaadamantane derivatives.…”

Section: Methods Of the Synthesis Of Azaadamantanesmentioning

confidence: 99%

Azaadamantanes, a New Promising Scaffold for Medical Chemistry

et al. 2021

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Azaadamantanes are nitrogen-containing analogs of adamantane, which contain one or more nitrogen atoms instead of carbon atoms. This substitution leads to several specific chemical and physical properties. The azaadamantane derivatives have less lipophilicity compared to their adamantane analogs, which affects both their interaction with biological targets and bioavailability. The significant increase in the number of publications during the last decade (2009–2020) concerning the study of reactivity and biological activity of azaadamantanes and their derivatives indicates a great theoretical and practical interest in these compounds. Compounds with pronounced biological activity have been already discovered among azaadamantane derivatives. The review is devoted to the biological activity of azaadamantanes and their derivatives. It presents the main methods for the synthesis of di- and triazaadamantanes and summarizes the accumulated data on studying the biological activity of these compounds. The prospects for the use of azaadamantanes in medical chemistry and pharmacology are discussed.

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2,4,9‐Triazaadamantanes with “Clickable” Groups: Synthesis, Structure and Applications as Tripodal Platforms

Cited by 7 publications

References 90 publications

Revealing the Structure of Transition Metal Complexes of Formaldoxime

Revealing the Structure of Transition Metal Complexes of Formaldoxime

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

Azaadamantanes, a New Promising Scaffold for Medical Chemistry

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