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Catalysis of Selective Hydrogen/Deuterium Exchange at Allylic Positions Using Deuterium Oxide

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Abstract

Deuterated organic compounds can be prepared efficiently and cost effectively by the direct exchange of a hydrogen atom by a deuterium atom on a carbon center rather than classical synthetic procedures. H/D exchange is achieved at allylic positions of alkenes catalyzed by alkene isomerization catalyst 1. An outstanding degree of deuteration is achieved at positions accessible by isomerization in homogeneous and biphasic reaction settings.

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Notes

  1. The effects of isotope fractionation have been considered. Experimental data summarized in Table 9 of ref. 23 for ethylene and methane suggest that insignificant fractionation between vinylic and alkyl C–H bonds should occur, and the effect of fractionation between these hydrocarbon C–H bonds and the O–H bonds should have less than 1–2% effect on degree of substrate deuteration under our conditions.

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Acknowledgements

We thank Reji Nair for early experiments, Dr. LeRoy Lafferty for his assistance with NMR experiments, and the NSF (CHE 0719575) for supporting this and related work.

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, San Diego State University, 5500 Campanile Drive, San Diego, CA, 92182-1030, USA

    Gulin Erdogan & Douglas B. Grotjahn

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  1. Gulin Erdogan
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  2. Douglas B. Grotjahn
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Correspondence to Douglas B. Grotjahn.

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Erdogan, G., Grotjahn, D.B. Catalysis of Selective Hydrogen/Deuterium Exchange at Allylic Positions Using Deuterium Oxide. Top Catal 53, 1055–1058 (2010). https://doi.org/10.1007/s11244-010-9531-7

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