Convenient synthesis of new tetraazamacrocycle-based macrobicycles

Brandès, Stéphane; Lacour, Sylvie; Denat, Franck; Pullumbi, Pluton; Guilard, Roger

doi:10.1039/a708390d

Cited by 25 publications

(14 citation statements)

References 17 publications

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“…Method A is rarely used to synthesize macro-unsymmetrical macrotricycles 5, 6, and 15 are obtained in 63Ϫ80% yield, respectively, by reacting 1.1 equiv. of α,αЈ-Moreover, we have prepared macrobicyclic ligands [69] of the cyclam or cyclen series using the corresponding nondibromo-m-(or -p)-xylene with the bis(macrocycle) in acetonitrile. The reaction is carried out under high dilution con-protected macrocycle as a starting material (Scheme 4).…”

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confidence: 99%

“…[68] [69] and cylindrical macrotricyclic [70] [71] ligands starting from cyclam Synthesis (1,4,8,11-tetraazacyclotetradecane) or dioxo macrocycles, in order to avoid the use of the usual protecting groups. We Several strategies for synthesizing cylindrical macrotricycles may be considered, and these are represented in describe herein in detail the methods of synthesis of these new cylindrical macrotricycle ligands in a face-to-face ar-Scheme 1.…”

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Synthesis of Macropolycyclic Ligands Based on Tetraazacycloalkanes

Brandès¹,

Denat²,

Lacour³

et al. 1998

Eur. J. Org. Chem.

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A versatile synthesis of spherical macrobicyclic and cylindrical macrotricyclic ligands is described using 1,4,8,11‐tetraazacyclotetradecane (cyclam), 1,4,7,10‐tetraazacyclododecane (cyclen), or dioxo macrocycles as precursors. Macrobicycles have been obtained by allowing cyclam, cyclen, or 5,12‐dioxocyclam (1,4,8,11‐tetraazacyclotetradecane‐5,12‐dione) to react with a bis‐electrophilic spacer under high dilution conditions. A surprising selectivity has been observed for 2,6‐dioxocyclen (1,4,7,10‐tetraazacyclododecane‐2,6‐dione), which yields only macrotricycles under the same reaction conditions. Molecular modelling studies have been carried out to investigate the selectivity of the reactions, and good agreement has been observed between the theoretical predictions and experimental data. 1D‐ and 2D‐NMR studies reveal a highly rigid structure in the case of macrobicycles. The macropolycyclic ligands show very different basicities, which demonstrates the influence of the cross‐linker on the coordination properties of the ligands.

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confidence: 99%

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confidence: 99%

Synthesis of Macropolycyclic Ligands Based on Tetraazacycloalkanes

Brandès¹,

Denat²,

Lacour³

et al. 1998

Eur. J. Org. Chem.

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“…The boc groups were then cleaved with HCl/methanol to afford 7 in 50% overall yield. It needs to be noted that alternative syntheses for 7 using high dilution [15] and boron-protection [14] procedures have been reported previously. Finally, reduction of 7 to yield 8 has also been reported recently [11] involving H 2 (3 atm.…”

Section: Introductionmentioning

confidence: 97%

“…Alkylation of the tri-N-boc protected derivative of cyclam 5 [14] with 4-nitrobenzyl bromide in the presence of caesium carbonate, followed by purification by column chromatography, yielded 6. The boc groups were then cleaved with HCl/methanol to afford 7 in 50% overall yield.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of one-, two- and three-ring macrocyclic, bifunctional compounds for use in radiolabelling monoclonal antibodies

Rami

Dong

Lindoy

et al. 2005

Journal of Heterocyclic Chemistry

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“…Finally, under high dilution conditions, direct reaction of cyclam with bis-electrophiles gave macrobicyclic ligands possessing tertiary amines at N 1 and N 8 . [16,17] Another approach toward selective functionalization, without protection, relies on the unusual properties of tetraazamacrocycles which have two basic and two nonbasic nitrogen atoms so that two nitrogen atoms can be temporarily protected by protons. A pH-controlled reaction between 1,4,7,10-tetraazacyclododecane (cyclen) and chloroformates has been achieved at an appropriate pH (pH ϭ 2Ϫ3).…”

Section: Introductionmentioning

confidence: 99%

A Tunable One‐Step N,N′‐Disubstitution of 1,4,8,11‐Tetraazacyclotetradecane with Acrylamide

2003

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N,N′‐disubstitution of cyclam without the use of protecting groups was investigated. This macrocycle reacted with two equivalents of a Michael acceptor in chloroform to yield as a major isolated compound the 1,8 di‐N,N′‐substituted macrocycle. Running the same reaction in the presence of one equivalent of para‐toluenesulfonic acid led to the 1,11‐di‐N,N′‐substituted macrocycle as the major product. Each regioisomer has been isolated and fully characterized. The observed regioselectivity is discussed with respect to the reactivity of the unprotonated or protonated monoalkylated intermediate. A site of protonation for the latter intermediate is deduced from an NMR study. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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Convenient synthesis of new tetraazamacrocycle-based macrobicycles

Cited by 25 publications

References 17 publications

Synthesis of Macropolycyclic Ligands Based on Tetraazacycloalkanes

Synthesis of Macropolycyclic Ligands Based on Tetraazacycloalkanes

Synthesis of one-, two- and three-ring macrocyclic, bifunctional compounds for use in radiolabelling monoclonal antibodies

A Tunable One‐Step N,N′‐Disubstitution of 1,4,8,11‐Tetraazacyclotetradecane with Acrylamide

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