Metal chelation with natural products: isomaltol complexes of aluminum, gallium, and indium

Lutz, Tammy G.; Clevette, David J.; Rettig, Steven J.; Orvig, Chris

doi:10.1021/ic00303a021

Cited by 26 publications

(20 citation statements)

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“…It was our interest in maltol as an effective bidentate chelating ligand for group 13 metal ions (16,17) that instigated the investigation of its structural isomer, isomaltol, as yet another naturally occurring bidentate chelator (18). However, once it was established that isomaltol was not a good ligand for the formation of other hexadentate ligands (i.e., its denticity cannot be increased via an imine linkage), due to nucleophilic attack being favored at the C-5 carbon (19), attention was turned to using the amide linkage both as a metal binding group, as well as the "arm" to increase the denticity of the ligand.…”

Section: Introductionmentioning

confidence: 99%

Tripodal trisamides based on nicotinic and picolinic acid derivatives

Hoveyda¹,

Karunaratne²,

Nichols³

et al. 1998

Can. J. Chem.

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A number of polydentate arylamide ligands have been prepared by coupling various acyclic tripodal or linear polyamines with derivatives of nicotinic and picolinic acids. Two synthetic procedures were utilized; tris{[(2-hydroxynicotinyl)carbonyl]-2-aminoethyl}amine (H 3 NICTREN) was prepared by Method A, the HOSu/DCC method, and the other arylamides in this study were prepared by Method B, the CDI method. Method A involved the reaction of N-hydroxysuccinimide with 2-hydroxynicotinic acid (in the presence of dicyclohexylcarbodiimide (DCC) as a dehydrative coupling reagent) to form the succinimide ester, followed by reaction with TREN to yield H 3 NICTREN. Method B involved reaction of a carboxylic acid (2-hydroxynicotinic, 3-hydroxypicolinic, nicotinic, or picolinic acids) with carbonyldiimidazole (CDI) to form the N-acylimidazolide, followed by reaction with the amine (TREN, TAME, spermidine, or TRPN) to yield the desired arylamide. The X-ray structure of 1,1,1-tris{[(3-hydroxypicolinyl)carbonyl]-2-aminomethyl}ethane (H 3 PICTAME) was determined; crystals of H 3 PICTAME are monoclinic, a = 10.257(2), b = 15.572 (3), c = 15.208(2) Å, β = 96.124(15)°, Z = 4, space group P2 1 /a. The structure was solved by direct methods and refined by full-matrix least-squares procedures to R = 0.041 and R w = 0.038 for 2506 reflections with I ≥ 3σ(I). In the solid state, H 3 PICTAME contains an extensive hydrogen-bonding network, with eight intra-and one intermolecular H-bonds per molecule; the ligand is partially preorganized for metal ion chelation. The acid dissociation constants of H 3 NICTREN and those of 1,1,1-tris{[(2-hydroxynicotinyl)carbonyl]-2-aminomethyl}ethane (H 3 NICTAME) have been determined; pK a1 = 11.2 (10.68), pK a2 = 10.7 (10.58), pK a3 = 10.0 (9.71), and pK a4 = 6.25 for H 3 NICTREN (H 3 NICTAME); the high phenolic pK a 's are consistent with the hydrogen bonding observed in the solid state.Résumé : On a préparé une série de ligands arylamides polydentates en procédant au couplage de diverses polyamines linéaires ou acycliques tripodaux avec des dérivés des acides nicotinique et picolinique. On a fait appel à deux voies de synthèse : on a préparé la tris{[(2-hydroxynicotinyl)carbonyl]-2-aminoéthyl}amine (H 3 NICTREN) par la méthode A, la méthode au HOSu/DCC, alors que les autres arylamides examinés dans cette étude ont été préparés par la méthode B, la méthode CDI. La méthode A implique la réaction du N-hydroxysuccinimide avec l'acide 2-hydroxynicotinique (en présence de dicyclohexylcarbodiimide (DCC) comme agent de couplage déshydratant) qui conduit à l'ester succinimide, suivie d'une réaction avec du « TREN » pour obtenir le H 3 NICTREN. La méthode B implique la réaction d'un acide carboxylique (acides 2-hydroxynicotinique, 3-hydroxypicolinique, nicotinique ou picolinique) avec le carbonyldiimidazole (CDI) pour former le N-acylimidazolide, suivie d'une réaction avec l'amine (« TREN », « TAME », spermidine ou « TRPN ») conduisant à l'arylamide désiré. On a déterminé la structure cristalline du 1,1,1-tris{[(3-...

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Section: Introductionmentioning

confidence: 99%

Tripodal trisamides based on nicotinic and picolinic acid derivatives

Hoveyda¹,

Karunaratne²,

Nichols³

et al. 1998

Can. J. Chem.

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“…Hehm also has two strong bands occurring at 1670 and 1630 cm-' corresponding to C=O and C=C stretches, respectively (28). The sive conjugation and hydrogen bonding with the hydroxyl hydrogen, analogous to that seen with isomaltol (9). There are three bands in the C-0 stretch region at 1260, 1180, and 1080 cm-I, but it is not possible to assign any one band due to ring vibrations and C-H bending modes occurring in the same region.…”

Section: Results and Discussion Hehmmentioning

confidence: 91%

“…These were mostly as previously described (4,6,8,9). Dimethylsulfide (Aldrich), ethyl bromoacetate (Aldrich), methylamine (40% in H20 -Fisher), and A1(N03)3.9H20 (Mallinckrodt) were used as supplied.…”

Section: Methodsmentioning

confidence: 99%

“…Potentiometric measurements (at p = 0.6 or 0.15 M NaCl for the All Hahm system; at p = 0.15 M NaCl for the Ga/Hahm system) of the ligand in the absence, and presence, of metal ions were performed as described previously (9,15). The temperature was maintained at 25.0 2 O.l°C throughout.…”

Section: Potentiometric Equilibrium Measurementsmentioning

confidence: 99%

“…These complexes are tris(bidentate ligand)metal(III) species, and incorporate as ligands various pyrones (e.g. maltol, 1) (4, 5 ) , N-substituted-3-hydroxy-4-pyridinones (2) (6)(7)(8) and isomaltol (3) (9). The properties of interest are hydrolytic stability, water solubility, neutral charge, and lipophilicity, all occurring simultaneously.…”

Section: Introductionmentioning

confidence: 99%

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Preparation of 2- and 4-substituted 3-hydroxy-5-methylfurans and the aluminum and gallium complexes of 3-hydroxy-5-methyl-2-(N-methylformamido)furan

Lutz¹,

Clevette²,

Hoveyda³

et al. 1994

Can. J. Chem.

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Can. J. Chem. 72, 1362 (1994.In model studies designed to study the synthesis of potentially hexadentate chelates based on the linkage of three furan rings to a triamine via amide linkages, new 2-and 4-substituted 3-hydroxy-5-methylfurans have been prepared. Particularly, 3-hydroxy-5-methyl-(N-methylforrnamido)furan (Hahm) and its Al and Ga complexes (M(ahm)3) have been prepared and thoroughly characterized by a variety of techniques, in the solid state and in solution. Solution equilibrium studies ( p = 0.6 M NaCl, 25°C) uncovered a complicated set of equilibria in the ~l~+ / H a h m system; the solution potentiometric data were best explained by the presence of mixed ligand (

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Characterization of aluminium complexes in tea extract. Part I—²⁷Al NMR studies

Mhatre

Iyer

Moorthy

1993

Magnetic Reson in Chemistry

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The high-field "AI NMR spectrum of aqueous tea extract contained two narrow resonances a t 9.85 and 16.15 ppm. The spectra of aluminium chelates with a number of model ligands (catechol, pyrogallol, catechin, kojic acid, protocatechuic acid, ascorbic acid and salicylic acid) containing chelating moieties present in the constituents of tea showed broad resonances in the range 8-36 ppm. Potentiometric and NMR studies indicate the formation of a monohydroxo 1 : 1 Akatechin chelate (6 8.3 ppm) with highly distorted symmetry. From a comparison of the NMR spectra of tea infusions a t different p H values with those of aluminium chelates with malic acid and oxalic acid (minor constituents in tea), the resonance at 16.15 ppm was assigned to the highly symmetric octahedral anionic chelate trisoxalatoaluminium, [ Al(C,O,), 1 '-. This was confirmed by anion-exchange separation of the chelate and its identification by 27Al NMR spectroscopy. The signal a t 9.8 ppm could be due to a mixed ligand chelate containing oxalate. In the case of the aluminiuwmalate system, the resonance a t 20 ppm was assigned to a 1 : 2 chelate in which malate functions as a tridentate resulting in five-and six-membered chelate rings.

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Metal chelation with natural products: isomaltol complexes of aluminum, gallium, and indium

Cited by 26 publications

References 2 publications

Tripodal trisamides based on nicotinic and picolinic acid derivatives

Tripodal trisamides based on nicotinic and picolinic acid derivatives

Preparation of 2- and 4-substituted 3-hydroxy-5-methylfurans and the aluminum and gallium complexes of 3-hydroxy-5-methyl-2-(N-methylformamido)furan

Characterization of aluminium complexes in tea extract. Part I—²⁷Al NMR studies

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Metal chelation with natural products: isomaltol complexes of aluminum, gallium, and indium

Cited by 26 publications

References 2 publications

Tripodal trisamides based on nicotinic and picolinic acid derivatives

Tripodal trisamides based on nicotinic and picolinic acid derivatives

Preparation of 2- and 4-substituted 3-hydroxy-5-methylfurans and the aluminum and gallium complexes of 3-hydroxy-5-methyl-2-(N-methylformamido)furan

Characterization of aluminium complexes in tea extract. Part I—27Al NMR studies

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Characterization of aluminium complexes in tea extract. Part I—²⁷Al NMR studies