- Scalable and selective deuteration of (hetero)arenes
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Isotope labelling, particularly deuteration, is an important tool for the development of new drugs, specifically for identification and quantification of metabolites. For this purpose, many efficient methodologies have been developed that allow for the small-scale synthesis of selectively deuterated compounds. Due to the development of deuterated compounds as active drug ingredients, there is a growing interest in scalable methods for deuteration. The development of methodologies for large-scale deuterium labelling in industrial settings requires technologies that are reliable, robust and scalable. Here we show that a nanostructured iron catalyst, prepared by combining cellulose with abundant iron salts, permits the selective deuteration of (hetero)arenes including anilines, phenols, indoles and other heterocycles, using inexpensive D2O under hydrogen pressure. This methodology represents an easily scalable deuteration (demonstrated by the synthesis of deuterium-containing products on the kilogram scale) and the air- and water-stable catalyst enables efficient labelling in a straightforward manner with high quality control. [Figure not available: see fulltext.].
- Bartling, Stephan,Beller, Matthias,Bourriquen, Florian,Brückner, Angelika,Junge, Kathrin,Kreyenschulte, Carsten,Lei, Aiwen,Li, Wu,Lund, Henrik,Rabeah, Jabor,Rockstroh, Nils,Surkus, Annette-Enrica,Yang, Dali
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- Sytheses and ENDOR Studies of Selectively Deuterated Galvinoxyl Radicals. Complete Determination of the 13C Hyperfine Coupling Constants of Coppingers's Radical
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The synthesis of selectively deuterated galvinols is described.Oxidation results in the formation of the respective galvinoxyl free radicals, e.g., Coppinger's radical and Yang's biradical.It is shown that 13C ENDOR signals can be detected for the doublet radicals without 13C labelling, i.e., in natural abundance.The complete set of 13C hyperfine coupling constants of Coppinger's radical could be determined.The ENDOR study of selectively deuterated Yang's biradical in a glassy matrix allowed an unambiguous assignment of the signals to molecular positions, and conclusions with respect to the symmetry of the radical and the hindered rotation of the tert-butyl groups could be drawn.Randomly oriented bisgalvinoxyl biradicals in the triplet spin state give rise to sharp ENDOR lines at the free nuclear Zeeman frequencies due to NMR transitions in the MS=0 electron spin manifold, and it is demonstrated that the respective 2H ENDOR lines show quadrupole splittings.
- Kirste, Burkhard,Kurrek, Harry,Sordo, Magdalena
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p. 1782 - 1797
(2007/10/02)
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