Photochemical Preparation of 1,3,5,7-Tetracyanoadamantane and Its Conversion to 1,3,5,7-Tetrakis(aminomethyl)adamantane

Lee, Ging S.; Bashara, Jude N.; Sabih, Ghiwa; Oganesyan, Asmik; Godjoian, Gayane; Duong, Hieu M.; Marinez, Eric R.; Gutiérrez, Carlos Gutièrrez

doi:10.1021/ol036526g

Cited by 35 publications

(37 citation statements)

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“…26 However, 1,3,5,7-tetrabromoadamantane is the most chemically inert entity in the row and the substitution of halogens via the S N1 mechanism demands harsh conditions. It was not only until the recent paper of Lee et al, 27 in which photochemical cyanodebromination of 1,3,5,7-tetrabromoadamantane was described that a facile route to various tetrasubstituted adamantanes, including the fundamental 1,3,5,7-tetracarboxyadamantane, became available. 'Click chemistry' of tetrazole formation, 28,29 by cycloaddition of azides to nitriles in the presence of ZnCl 2 makes the tetrakis-tetrazole derivative of adamantane especially affordable (Scheme 2).…”

Section: The Ligandmentioning

confidence: 99%

“…The thermogravimetric (TG-DTA) analyses were performed using a Netzsch STA 449 C Jupiter instrument coupled with a Pfeiffer Thermostar GSD 300 mass spectrometer at 5-10°C min −1 heating rate under inert gas flow using corundum sample holders. Alternatively, the TG data were collected using a Netzsch 209 F3 Tarsus instrument in a protecting flow of nitrogen (10 ml min −1 ) at 27 and 28.4 g sodium azide in 500 ml of DMF, 39.6 g of anhydrous ZnCl 2 was added under stirring. The formed mixture was refluxed for 48 h maintaining anhydrous conditions.…”

Section: Analyticsmentioning

confidence: 99%

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1,3,5,7-Tetrakis(tetrazol-5-yl)-adamantane: the smallest tetrahedral tetrazole-functionalized ligand and its complexes formed by reaction with anhydrous M(ii)Cl₂(M = Mn, Cu, Zn, Cd)

et al. 2014

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·62 ·8}, gis or gismondine underlying net, where the role of the tetrahedral nodes is served by the coordination bonded clusters and the adamantane moiety. 3 (P2 1 /n) has a porous structure composed of coordination bonded layers with a (4·8 2 ) fes topology joined via trans-{Zn- The high number of donor functions endows the tetrazolate function with a capability to sustain unusually high number of coordination bonded arrangements ( patterns) 7 compared to other azolates. In the case of simple rigid ligands it is a prerequisite for assembly of a highly symmetric framework, with a † Dedicated to Prof. Marius Andruh on the occasion of his 60th birthday. View Article OnlineView Journal | View Issue significant probability of isomerism. Indeed, the linear 1,4-benzeneditetrazole (H 2 BDT) 8 and flat triangular 1,3,5-benzene- hedral' tetrazolates and involving chloride anions as coligands, serve as an interesting example of variability of coordination-bonded cluster geometry and size due to involvement of short halido bridges. 16,20 It was conjectured that mixed tetrazolato/halido coordination polymers constitute an interesting compound class with 'scalable' multinuclear clusters, 20 which are interesting either as robust SBUs or possibly as functional magnetic units. In this contribution we probed the practically unexplored 1,3,5,7-tetrakis(tetrazol-5yl)adamantane ligand (H 4 L) as a building block for coordination polymers using conditions favoring formation of tetrazolato/halido clusters (Scheme 1). This ligand in anionic form has one of the highest density of donor sites achievable for a 'tetrahedral' ligand, which is a prerequisite for rich coordination and structural chemistry of derived coordination-bonded frameworks. Results and discussion The ligandUniversal rigid molecular platforms with tetrahedral symmetry are typically limited to tetraphenylmethane (including 9,9′-spirobifluorene) and adamantane, as well as their phenyl augmented and heteroatom-substituted analogues.14 Adamantane is the smallest tetrahedral platform next only to quaternary carbon, while the latter has inherent steric limitations. Adamantane is widely used for the synthesis of organic polymers (recently with an emphasis on porous organic polymers and covalent organic frameworks), 22 dendrimers, 23 and molecular entities for supramolecular synthesis 24 and nanotechnology. 25Compared to tetraphenylmethane, whose modification is standard and facile, the chemistry of adamantanes is peculiar, at times cumbersome, but offering synthetic opportunities as well. For example adamantane could be selectively brominated in bridgehead positions to afford mono-to tetra-substituted adamantanes in high yields. 26 However, 1,3,5,7-tetrabromoadamantane is the most chemically inert entity in the row and the substitution of halogens via the S N1 mechanism demands harsh conditions. It was not only until the recent paper of Lee et al.,27 in which photochemical cyanodebromination of 1,3,5,7-tetrabromoadamantane was described that a facile route to various tetra...

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Section: The Ligandmentioning

confidence: 99%

Section: Analyticsmentioning

confidence: 99%

1,3,5,7-Tetrakis(tetrazol-5-yl)-adamantane: the smallest tetrahedral tetrazole-functionalized ligand and its complexes formed by reaction with anhydrous M(ii)Cl₂(M = Mn, Cu, Zn, Cd)

et al. 2014

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“…90) [187]. On the other hand, several 9,10-dihalotriptycenes (9,10-dibromo, 9-bromo-10-iodo and 9-bromo-10-chloro) react with LiSnMe 3 to afford monosubstitution (12-66%) and disubstitution (10-65%) through competition between polar and radical pathways (eq.…”

Section: Bridgehead Halidesmentioning

confidence: 99%

Strategies in Synthetic Radical Organic Chemistry. Recent Advances on Cyclization and SRN1 Reactions

Rossi¹,

Peñéñory

2006

COS

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“…The synthesis of tetra‐halogenated compounds with the same halogen at each bridgehead position is performed in one single step (Table : compounds 1 , 2, and 3 ) . However, these products are quite difficult to functionalize to obtain more complex structures due to low solubility and reactivity.…”

Section: Introductionmentioning

confidence: 99%

Multifunctional adamantane derivatives as new scaffolds for the multipresentation of bioactive peptides

Grillaud

Bianco

2014

Journal of Peptide Science

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The remarkable structural and chemical properties of adamantane afford attractive opportunities to design various adamantane-based scaffolds for biomedical applications. A wide range of mono-functionalized adamantane compounds have already been investigated and reviewed, mostly as anti-viral agents. The four bridgehead positions of adamantane provide many possibilities to design poly-functional derivatives, and the recent conception of adamantane building blocks with multiple substituents has shown promising applications in several domains. In this review, we provide a detailed description of the different ways to synthesize multifunctional derivatives starting from adamantane molecule as the main core. We will then describe the interesting biological activity of the diverse multivalent scaffolds, focusing in particular on peptide-based systems. The results reported here will certainly encourage the development of novel adamantane-based structures for biological purposes.

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Photochemical Preparation of 1,3,5,7-Tetracyanoadamantane and Its Conversion to 1,3,5,7-Tetrakis(aminomethyl)adamantane

Cited by 35 publications

References 23 publications

1,3,5,7-Tetrakis(tetrazol-5-yl)-adamantane: the smallest tetrahedral tetrazole-functionalized ligand and its complexes formed by reaction with anhydrous M(ii)Cl₂(M = Mn, Cu, Zn, Cd)

1,3,5,7-Tetrakis(tetrazol-5-yl)-adamantane: the smallest tetrahedral tetrazole-functionalized ligand and its complexes formed by reaction with anhydrous M(ii)Cl₂(M = Mn, Cu, Zn, Cd)

Strategies in Synthetic Radical Organic Chemistry. Recent Advances on Cyclization and SRN1 Reactions

Multifunctional adamantane derivatives as new scaffolds for the multipresentation of bioactive peptides

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Photochemical Preparation of 1,3,5,7-Tetracyanoadamantane and Its Conversion to 1,3,5,7-Tetrakis(aminomethyl)adamantane

Cited by 35 publications

References 23 publications

1,3,5,7-Tetrakis(tetrazol-5-yl)-adamantane: the smallest tetrahedral tetrazole-functionalized ligand and its complexes formed by reaction with anhydrous M(ii)Cl2(M = Mn, Cu, Zn, Cd)

1,3,5,7-Tetrakis(tetrazol-5-yl)-adamantane: the smallest tetrahedral tetrazole-functionalized ligand and its complexes formed by reaction with anhydrous M(ii)Cl2(M = Mn, Cu, Zn, Cd)

Strategies in Synthetic Radical Organic Chemistry. Recent Advances on Cyclization and SRN1 Reactions

Multifunctional adamantane derivatives as new scaffolds for the multipresentation of bioactive peptides

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1,3,5,7-Tetrakis(tetrazol-5-yl)-adamantane: the smallest tetrahedral tetrazole-functionalized ligand and its complexes formed by reaction with anhydrous M(ii)Cl₂(M = Mn, Cu, Zn, Cd)

1,3,5,7-Tetrakis(tetrazol-5-yl)-adamantane: the smallest tetrahedral tetrazole-functionalized ligand and its complexes formed by reaction with anhydrous M(ii)Cl₂(M = Mn, Cu, Zn, Cd)