A solid-phase iridium-based ortho-exchange catalyst for the one-step labelling of aromatic substrates with deuterium

Hickey, Michael J.; Jones, John R.; Kingston, Lee P.; Lockley, W. J. S.; Mather, A. N.; Wilkinson, David J.

doi:10.1016/j.tetlet.2004.09.159

Cited by 29 publications

(13 citation statements)

References 14 publications

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“…More recent publications describe the immobilization of catalysts on a polymer support, [62] reaction acceleration in microwave synthesis apparatus, [53d, 63] the use of ionic liquids as cosolvents, [56] and the use of Raman spectroscopy for monitoring isotope exchange in real time. [64] The use of soluble iridium complexes for H/T exchange has also been described.…”

Section: Angewandte Chemiementioning

confidence: 99%

The Renaissance of H/D Exchange

Atzrodt¹,

Derdau²,

Fey³

et al. 2007

Angew Chem Int Ed

603

324

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The increasing demand for stable isotopically labeled compounds has led to an increased interest in H/D-exchange reactions at carbon centers. Today deuterium-labeled compounds are used as internal standards in mass spectrometry or to help elucidate mechanistic theories. Access to these deuterated compounds takes place significantly more efficiently and more cost effectively by exchange of hydrogen by deuterium in the target molecule than by classical synthesis. This Review will concentrate on the preparative application of the H/D-exchange reaction in the preparation of deuterium-labeled compounds. Advances over the last ten years are brought together and critically evaluated.

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Section: Angewandte Chemiementioning

confidence: 99%

The Renaissance of H/D Exchange

Atzrodt¹,

Derdau²,

Fey³

et al. 2007

Angew Chem Int Ed

603

324

View full text Add to dashboard Cite

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“…Neuere Veröffentlichungen beschreiben die Immobilisierung des Katalysators an einem polymeren Träger, [62] die Reaktionsbeschleunigung in Mikrowellensynthesegerä-ten, [53d, 63] die Verwendung ionischer Flüssigkeiten als Cosolventien [56] sowie den Einsatz der Raman-Spektroskopie zur Verfolgung des Isotopenaustausches in Echtzeit. [64] Auch die Verwendung löslicher Iridiumkomplexe zum H/T-Austausch wurde beschrieben.…”

Section: Iridium-katalysierter H/d-austauschunclassified

Die Renaissance des H/D‐Austausches

et al. 2007

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Die steigende Nachfrage nach stabil isotopenmarkierten Verbindungen führt zu einem verstärkten Interesse an H/D‐Austauschreaktionen an Kohlenstoffatomen. Heutzutage werden Deuterium‐markierte Verbindungen als interne Standards in der Massenspektrometrie eingesetzt oder helfen dabei, mechanistische Theorien zu untermauern. Der Zugang zu diesen deuterierten Verbindungen erfolgt über einen Austausch von Wasserstoff gegen Deuterium im Zielmolekül deutlich effizienter und preiswerter als über die klassische Synthese. Schwerpunkt dieses Aufsatzes sind präparative Anwendungen der H/D‐Austauschreaktion zur Herstellung Deuterium‐markierter Substanzen. Die Fortschritte der letzten zehn Jahre werden zusammengefasst und kritisch bewertet.

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“…Advantages to this method include the ready accessibility of halogenated derivatives 86 , the versatility of the method, achievement of high specific activities and the relative certainty as to the location of tritium so introduced. A vast number of synthetic, bioactive compounds and research tools have been prepared this way.…”

Section: Tritiodehalogenations 8485mentioning

confidence: 99%

Preparation of Tritium‐Labeled Compounds by Chemical Synthesis

2009

Preparation of Compounds Labeled With Tritium and Carbon‐14

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In contrast to isotope exchange methods, which utilize the target compound or a late intermediate as substrate for labeling, chemical synthesis involves transformation of some precursor chemical with concurrent introduction of tritium. Four basic types of transformations are distinguished for discussion each in turn. They are catalytic tritiations (Section 4.1), which usually involve the reduction of a precursor compound using a catalyst and tritium gas; catalytic tritiolyses (Section 4.2), involving the replacement of functional groups by tritium, again using a catalyst and tritium gas; tritide reductions (Section 4.3), utilizing tritiated versions of hydridic reducing reagents; and the use of small tritiated building blocks (Section 4.4) in synthetic operations to construct target molecules.A phenomenon strongly relevant to the catalytic methods discussed in Sections 4.1 and 4.2, and of some relevance also for tritide chemistry (Section 4.3) is solvent exchange. Most catalytic tritiations and tritiolyses are conducted in solution, and a wide variety of solvents have been used, ranging from nonpolar ones to highly polar, hydroxylic media. The properties of the solvent, however, influence not only the course and rate of a heterogeneously catalyzed reaction, but also the extent to which solvent hydrogen may exchange with tritium gas as a side reaction and thereby dilute the isotope introduced into the substrate: solvent exchange. It is commonly recognized that the use of protic solvents for tritiations and tritiolyses increases the risk of obtaining products of less than maximal specific activity, although it is equally clear that such reactions often succeed without dilution of label. The crucial factor in each experiment is the relationship between the rate of the tritium-incorporation reaction and the rate(s) of any tritium-diluting reaction(s). It is documented that the rate of metal-catalyzed exchange between elemental hydrogen and water is significant, especially at low pH 1 , but little quantitative data are available to guide practice. Recently a turnover number of 17.3 h À1 was reported for the exchange between H 2 and 2 H 2 O catalyzed by 10% Pd/C at room temperature and a pressure of 1 atm 2 ; this is rapid enough to provide the basis for an economical method of catalytic deuterium exchange Preparation of Compounds Labeled with Tritium and Carbon-14 Rolf Voges, J. Richard Heys and Thomas Moenius

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A solid-phase iridium-based ortho-exchange catalyst for the one-step labelling of aromatic substrates with deuterium

Cited by 29 publications

References 14 publications

The Renaissance of H/D Exchange

The Renaissance of H/D Exchange

Die Renaissance des H/D‐Austausches

Preparation of Tritium‐Labeled Compounds by Chemical Synthesis

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