exo-Diastereoisomer of 10-aryl-1,4,7-triazabicyclo[5.2.1]decane as intermediary in specific derivatisation of triazacyclononane

Roger, Mélissa; Patinec, Véronique; Bourgeois, Martine; Tripier, Raphaël; Triki, Smaı̈l; Handel, Henri

doi:10.1016/j.tet.2012.04.057

Cited by 12 publications

(12 citation statements)

References 39 publications

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“…Compounds 4 and 5 have been obtained following our previously described procedures. [22,24] tert-Butyl 2,2Ј,2ЈЈ-(10-{[6-(Chloromethyl)pyridin-2-yl]methyl}-1,4,7,10-tetraazacyclododecane-1,4,7-triyl)triacetate (3): A solution of DO3AtBu 1 (1.00 g, 1.94 mmol) in distilled acetonitrile (120 mL) was added dropwise over 1 h to a stirred solution of 2 (1.70 g, 9.70 mmol, 5.0 equiv.) and potassium carbonate (1.30 g, 9.70 mmol, 5.0 equiv.)…”

Section: Methodsmentioning

confidence: 99%

“…[23] The synthesis of the ligands was achieved following our previously described strategies. [22,24] Ligands H 3 L1 and H 3 L2 were synthesized starting from precursor DO3AtBu (1). Condensation of the latter with an excess amount of 2,6-bis(chloromethyl)pyridine (2) in the presence of K 2 CO 3 led, after workup with column chromatography on alumina, to the functionalized DO3AtBu derivative 3 with 33 % yield.…”

Section: Synthesismentioning

confidence: 99%

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Lanthanide Complexes with Heteroditopic Ligands as Fluorescent Zinc Sensors

et al. 2014

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International audienceWe report the synthesis of two ligands containing a DO3A unit (H3DO3A = 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid) linked to a triazacyclononane (TACN) moiety by a 2,6-dimethylpyridine spacer designed to form stable Ln3+ complexes in solution that respond to the presence of Zn2+ ions. The Eu3+ and Gd3+ complexes have been characterized by using a combination of experimental and theoretical techniques that include absorption and emission electronic spectroscopy, NMR spectroscopy, 1H relaxometry, and DFT calculations. The Ln3+ ions are eight-coordinated by the ligand, which binds to the metal ion through the seven donor atoms of the DO3A unit and the nitrogen atom of the pyridyl linker. Luminescence lifetime measurements recorded from solutions of the Eu3+ complexes in H2O and D2O and relaxometric measurements point to the absence of inner-sphere water molecules. The addition of Zn2+ causes important changes in the absorption spectra of the complexes that evidence the formation of both 1:1 and 2:1 (Ln3+/Zn2+) complex species. However, the emission lifetimes of the Eu3+ complexes and relaxivity experience weak changes, thus indicating that Zn2+ addition does not significantly affect the number of coordinated water molecules. The Gd3+ complexes show a weak emission band at 325 nm, the intensity of which dramatically increases in the presence of Zn2+. However, the “turn-on” behaviour induced by Zn2+ is not observed for other metal cations such as Ca2+, Mg2+ or Cu2+. DFT calculations indicate that a photoinduced electron-transfer (PET) process is responsible for the quenching of the luminescence in the absence of Zn2+

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Section: Methodsmentioning

confidence: 99%

Section: Synthesismentioning

confidence: 99%

Lanthanide Complexes with Heteroditopic Ligands as Fluorescent Zinc Sensors

et al. 2014

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“…To overcome this difficulty, we tried the method of TACN functionalization using the aminal protecting group. [19] According to a described method a bicyclic compound 14 was obtained in a high yield by reacting free TACN with benzaldehyde (Scheme 3). The reaction of compound 14 with 1 equiv.…”

Section: Resultsmentioning

confidence: 99%

“…13 (14). [19] A oneneck flask equipped with a magnetic stirrer was charged with 1,4,7-triazacyclononane (645 mg, 5 mmol), 120 ml of ethanol, freshly distilled benzaldehyde (0.5 ml, 4.9 mmol) was added followed by molecular sieves, the mixture was stirred for 6 h. The residue was filtered off, washed with ethanol (10 ml), combined organic fractions were evaporated in vacuo to give compound 14 as pale-yellow crystals, m.p. 103-104 °C.…”

Section: -((59-bis(3-bromobenzyl)-159-triazacyclododecan-1-yl)sulmentioning

confidence: 99%

“…1,4-Bis(3-bromobenzyl)-7-(naphthalene-2-ylmethyl)-1,4,7-triazacyclononane (18). A one-neck flask equipped with a magnetic stirrer was charged with compound 17 (200 mg, 0.743 mmol), dissolved in MeCN (4 ml), 3-bromobenzyl bromide (280 mg, 1.1 mmol) was added followed by K 2 CO 3 (345 mg, 2.5 mmol), the reaction was stirred for 24 h, the residue was filtered off, washed with CH 2 Cl 2 ( 5(1,3)-dibenzenacycloicosaphane (19). Obtained according to a general procedure for macrocyclization from compound 18 (121 mg, 0.2 mmol), trioxadiamine 10 (44 mg, 0.2 mmol) in the presence of Pd(dba) 2 (18 mg, 0.032 mmol), DavePhos ( , dioxane (1 ml) was added followed by tBuONa (86 mg, 0.9 mmol).…”

Section: -((59-bis(3-bromobenzyl)-159-triazacyclododecan-1-yl)sulmentioning

confidence: 99%

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Pd(0)-Catalyzed Amination in the Synthesis of Bicyclic Compounds Comprising Triazacycloalkane and Fluorophore Moieties

Averin¹,

Chernichenko²,

Shevchuk³

et al. 2018

MHC

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Direct introduction of one dansyl fluorophore group into the molecule of 1,4,7-triazacyclononane (TACN) and 1,5,9-triazacyclododecane (TACD) was shown to be possible followed by the modification of triazacycles with two bromobenzyl substituents. The resulting compounds were used in the Pd(0)-catalyzed macrocyclization reaction with 1,13-diaza-4,7,10-trioxatridecane to provide corresponding cryptands. The synthesis of bicyclic derivatives of TACN bearing naphthyl and acridinyl fluorophore groups was accomplished via an alternative procedure using aminal-protected TACN. The possibility to form tetracyclic compounds starting from N,N',N"-tris(3-bromobenzyl) substituted TACN was demonstrated. Three cryptands bearing dansyl fluorophore were tested as potential fluorescent chemosensors for metal cations and were found to act as molecular fluorescent probes for Cu(II) and Al(III) by total emission quenching in the presence of these cations.

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Multigram Four‐Step Synthesis of 1,4,7‐Triazacyclononanes with 2R_a/R_bN‐Functionalization Pattern by Starting from Diethylenetriamine

Gros

Hasserodt

2014

Eur J Org Chem

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Polyazamacrocycles and their derivatives are appreciated for the strength of their corresponding metal complexes. 1,4,7‐Triazacyclononane (TACN) derivatives have been employed in an ever increasing number of applications. To this day, all synthetic routes to TACN derivatives that have identical or differing substituents require the initial preparation of unprotected TACN. Herein, we report the four‐step synthesis of TACN derivatives that have a 2Ra/Rb N‐functionalization pattern by starting from diethylenetriamine and employing an organic template strategy.

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exo-Diastereoisomer of 10-aryl-1,4,7-triazabicyclo[5.2.1]decane as intermediary in specific derivatisation of triazacyclononane

Cited by 12 publications

References 39 publications

Lanthanide Complexes with Heteroditopic Ligands as Fluorescent Zinc Sensors

Lanthanide Complexes with Heteroditopic Ligands as Fluorescent Zinc Sensors

Pd(0)-Catalyzed Amination in the Synthesis of Bicyclic Compounds Comprising Triazacycloalkane and Fluorophore Moieties

Multigram Four‐Step Synthesis of 1,4,7‐Triazacyclononanes with 2R_a/R_bN‐Functionalization Pattern by Starting from Diethylenetriamine

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exo-Diastereoisomer of 10-aryl-1,4,7-triazabicyclo[5.2.1]decane as intermediary in specific derivatisation of triazacyclononane

Cited by 12 publications

References 39 publications

Lanthanide Complexes with Heteroditopic Ligands as Fluorescent Zinc Sensors

Lanthanide Complexes with Heteroditopic Ligands as Fluorescent Zinc Sensors

Pd(0)-Catalyzed Amination in the Synthesis of Bicyclic Compounds Comprising Triazacycloalkane and Fluorophore Moieties

Multigram Four‐Step Synthesis of 1,4,7‐Triazacyclononanes with 2Ra/RbN‐Functionalization Pattern by Starting from Diethylenetriamine

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Multigram Four‐Step Synthesis of 1,4,7‐Triazacyclononanes with 2R_a/R_bN‐Functionalization Pattern by Starting from Diethylenetriamine