Rhodium‐ and ruthenium‐catalysed hydrogen isotope exchange

Lockley, W. J. S.; Hesk, David

doi:10.1002/jlcr.1815

Cited by 39 publications

(24 citation statements)

References 52 publications

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“…5b To determine the viability of a palladium-catalyzed H-D exchange method using a ketone as a directing group, 2-acetonaphthone was subjected to reaction with CF 3 COOD in the presence of several different palladium(II) complexes and additives (Table 1). …”

Section: Resultsmentioning

confidence: 99%

“…Acetanilides have been extensively utilized as directing groups for palladium-catalyzed C-H functionalization reactions and have also been employed to direct H-D exchange reactions with rhodium, 10c iridium, 11 and ruthenium. 5c The palladium-catalyzed ortho -selective H-D exchange of acetanilides was envisaged proceeding in a similar fashion to ketones under identical conditions. Our previous work 12 identified acetanilides as substrates well-suited for electrophilic H-D exchange in CF 3 COOD, so care was taken to identify any improvement in ortho -selective deuterium incorporation by catalyst 1 .…”

Section: Resultsmentioning

confidence: 99%

“…2 A number of catalytic processes have been investigated to produce these valuable deuterium-labeled compounds, including metal-free conditions as well as both homogeneous and heterogeneous metallic catalysts. 3 Of the homogenous transition metal-catalyzed methods for H-D exchange of pharmaceutically relevant compounds, most have focused on the use of rhodium and iridium 4 although H-D exchange of other small molecules by homogenous ruthenium, 5 palladium 5a,6 and platinum 5a,6b,7 species has also been reported. These reactions are frequently conducted in deuterated acidic media such as acetic acid-d 4 or trifluoroacetic acid-d 1 (CF 3 COOD).…”

Section: Introductionmentioning

confidence: 99%

“…However, recent studies have called into question whether certain metal-catalyzed H-D exchange reactions in acidic solvents proceed through C-H activation or electrophilic aromatic substitution mechanisms; in CF 3 COOD, the latter mechanism has been suggested to predominate. 5a,8 …”

Section: Introductionmentioning

confidence: 99%

“…A few reports of ligand-directed H-D exchange using rhodium 10 and ruthenium 5b–c catalysts have been published, although most studies employ iridium complexes. 11 Recently, a report of ligand-directed palladium-catalyzed ortho -selective H-D exchange of benzoic acids and phenylacetic acids using weak coordination has been published.…”

Section: Introductionmentioning

confidence: 99%

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H–D exchange in deuterated trifluoroacetic acid via ligand-directed NHC–palladium catalysis: a powerful method for deuteration of aromatic ketones, amides, and amino acids

Giles

Ahn

Jung

2015

Tetrahedron Letters

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A method has been developed for one-step ortho-selective ligand-directed H-D exchange, accompanied in some cases by concurrent acid-catalyzed electrophilic deuteration. This method is effective for deuteration of aromatic substrates ranging from ketones to amides and amino acids, including compounds of biological and pharmaceutical interest such as acetaminophen and edaravone. Use of a palladium catalyst featuring an NHC ligand is critical for the observed reactivity. Experimental evidence strongly suggests that palladium facilitates C-H activation of the aromatic substrates, a mechanism seldom observed under strongly acidic conditions. 2015 Elsevier Ltd. All rights reserved.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

H–D exchange in deuterated trifluoroacetic acid via ligand-directed NHC–palladium catalysis: a powerful method for deuteration of aromatic ketones, amides, and amino acids

Giles

Ahn

Jung

2015

Tetrahedron Letters

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Recent Advances in the Synthesis of Deuterium‐Labeled Compounds

2021

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Deuterium‐labeled compounds are of importance in chemical, environmental, and biological fields. Preparation methods for deuterium‐labeled compounds have been studied extensively in response to increasing demand for these chemicals. In this review, we summarize recent advances in synthetic methods and present a comprehensive overview of diverse routes, including conventional deuteration and hydrogen‐deuterium exchange. Deuteration by the classical process, which starts from appropriate available labeled precursors, is introduced for different reaction types. Key features of hydrogen‐deuterium exchange are elaborated in detail from the perspective of the catalyst and the chemical structure of the substrate. Regioselective deuteration at the target position is discussed because of the role of stereospecific deuterium labeling in medicine. Finally, challenges and future prospects of these processes are discussed to provide a general guideline for the synthesis of deuterium‐labeled compounds.

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Calcium Aluminate Induced Pt(0)‐Pt(δ+) Coupling Boost Catalyzed H−D Exchange Reaction of Arenes with Deuterium Oxide

et al. 2023

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Deuterium(D)‐labeled aromatics play an essential part in the Yield of fine chemicals. However, deuteration reactions are particularly dependent on the specific chemical environment of the metal to finish the oxidative addition and reductive elimination. Herein, a complex valence Pt/Ca12Al14Ox catalyst was successfully synthesized for the deuteration of toluene using inexpensive D2O. It exhibited high deuteration efficiency, achieving 96% deuteration in just 4 hours, 14% higher than the most commonly Pt/C catalyst. The catalyst can also be reactivated and recycled up to 16 times. Multiple characterization techniques were used to demonstrate the interaction between Pt and Ca12Al14Ox generates the co‐existence of Pt(δ+) and Pt(0). The synergy between Pt(δ+) and Pt(0) can promote the completion of oxidation and elimination reactions. Thus, the complex valence of Pt improves the processes required for H−D exchange and boosts the reaction rate and stability of the hydrogen isotope exchange system.

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Rhodium‐ and ruthenium‐catalysed hydrogen isotope exchange

Cited by 39 publications

References 52 publications

H–D exchange in deuterated trifluoroacetic acid via ligand-directed NHC–palladium catalysis: a powerful method for deuteration of aromatic ketones, amides, and amino acids

H–D exchange in deuterated trifluoroacetic acid via ligand-directed NHC–palladium catalysis: a powerful method for deuteration of aromatic ketones, amides, and amino acids

Recent Advances in the Synthesis of Deuterium‐Labeled Compounds

Calcium Aluminate Induced Pt(0)‐Pt(δ+) Coupling Boost Catalyzed H−D Exchange Reaction of Arenes with Deuterium Oxide

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