Homogeneous hydrogenation of electron-deficient alkenes by iridium complexes

Semeniuchenko, Volodymyr; Exner, Thomas E.; Khilya, Volodymyr; Groth, Ulrich

Homogeneous hydrogenation of electron-deficient alkenes by iridium complexes

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Date

2011

Authors

Semeniuchenko, Volodymyr

Exner, Thomas E.

Khilya, Volodymyr

Groth, Ulrich

Publication type

Journal article

Published in

Applied Organometallic Chemistry ; 25 (2011), 11. - pp. 804-809. - ISSN 0268-2605

Abstract

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.

Subject (DDC)

540 Chemistry

Keywords

hydrogenation,iridium,homogeneous catalysis,alkenes,density functional calculations

Cite This

ISO 690

SEMENIUCHENKO, Volodymyr, Thomas E. EXNER, Volodymyr KHILYA, Ulrich GROTH, 2011. Homogeneous hydrogenation of electron-deficient alkenes by iridium complexes. In: Applied Organometallic Chemistry. 25(11), pp. 804-809. ISSN 0268-2605. Available under: doi: 10.1002/aoc.1841

BibTex

@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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