Homogeneous hydrogenation of electron-deficient alkenes by iridium complexes

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2011
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Zusammenfassung

The catalytic homogeneous hydrogenation of electron-deficient alkenes (nucleophilic hydrogenation) was achieved in the presence of iridium complexes and a base as co-catalyst. Contrary to hydrogenation of electron-rich alkenes, which is inactivated by bases, the hydrogenation of the electron-deficient alkenes turned out to be base activated. Here, we present a more thorough study on the capacities but also limitations of this new reaction mechanism using screenings of the reaction conditions as well as different Ir complexes and substrates. The formation of a catalytically active Ir complex is proposed. The active complex usually attacks a soft electron-deficient atom, if more than one possibility exists (as shown by density functional theory computations). Additionally, first examples of enantiomeric enrichments in the presence of chiral Ir complexes are presented. The high catalyst load needed and the moderate yields show that the active complex is very unstable under conditions of nucleophilic hydrogenation and is quickly deactivated, which has to be addressed in further studies.

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540 Chemie
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hydrogenation, iridium, homogeneous catalysis, alkenes, density functional calculations
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ISO 690SEMENIUCHENKO, Volodymyr, Thomas E. EXNER, Volodymyr KHILYA, Ulrich GROTH, 2011. Homogeneous hydrogenation of electron-deficient alkenes by iridium complexes. In: Applied Organometallic Chemistry. 2011, 25(11), pp. 804-809. ISSN 0268-2605. Available under: doi: 10.1002/aoc.1841
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@article{Semeniuchenko2011Homog-17458,
  year={2011},
  doi={10.1002/aoc.1841},
  title={Homogeneous hydrogenation of electron-deficient alkenes by iridium complexes},
  number={11},
  volume={25},
  issn={0268-2605},
  journal={Applied Organometallic Chemistry},
  pages={804--809},
  author={Semeniuchenko, Volodymyr and Exner, Thomas E. and Khilya, Volodymyr and Groth, Ulrich}
}
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    <dcterms:abstract xml:lang="eng">The catalytic homogeneous hydrogenation of electron-deficient alkenes (nucleophilic hydrogenation) was achieved in the presence of iridium complexes and a base as co-catalyst. Contrary to hydrogenation of electron-rich alkenes, which is inactivated by bases, the hydrogenation of the electron-deficient alkenes turned out to be base activated. Here, we present a more thorough study on the capacities but also limitations of this new reaction mechanism using screenings of the reaction conditions as well as different Ir complexes and substrates. The formation of a catalytically active Ir complex is proposed. The active complex usually attacks a soft electron-deficient atom, if more than one possibility exists (as shown by density functional theory computations). Additionally, first examples of enantiomeric enrichments in the presence of chiral Ir complexes are presented. The high catalyst load needed and the moderate yields show that the active complex is very unstable under conditions of nucleophilic hydrogenation and is quickly deactivated, which has to be addressed in further studies.</dcterms:abstract>
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