Iridium-catalyzed enantioselective hydrogenation of imines in supercritical carbon dioxide

Kainz, S; Brinkmann, A; Leitner, W; Pfaltz, A

doi:10.1021/ja984309i

Title: Iridium-catalyzed enantioselective hydrogenation of imines in supercritical carbon dioxide

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Abstract

Supercritical carbon dioxide (scCO{sub 2}) was shown to be a reaction medium with unique properties for highly efficient iridium-catalyzed enantioselective hydrogenation of prochiral imines. Cationic iridium(I) complexes with chiral phosphinodihydrooxazoles, modified with perfluoroalkyl groups in the ligand or in the anion, were synthesized and tested in the hydrogenation of N-(1-phenylethylidene)aniline. Both the side chains and the lipophilic anions increased the solubility, but the choice of the anion also had a dramatic effect on the enantioselectivity with tetrakis-3,5-bis(trifluoromethyl)phenylborate (BARF) leading to the highest asymmetric induction. (R)-N-phenyl-1-phenylethylamine was formed quantitatively within 1 h in scCO{sub 2}[d(CO{sub 2}) = 0.75 g mL{sup {minus}1}] at 40 C and a H{sub 2} pressure of 30 bar with enantiomeric excesses of up to 81% using 0.078 mol % catalyst. The use of scCO{sub 2} instead of conventional solvents such as CH{sub 2}Cl{sub 2} allowed the catalyst loading to be lowered significantly owing to a change in the rate profile of the reaction. the homogeneous nature of the catalytically active species under the reaction conditions was demonstrated and was found to depend strongly on the composition of the reaction mixture and especially on the presence of the substrate. Utilizing the selective extractive properties of scCO{sub 2}, themore »« less

Authors:: Kainz, S; Brinkmann, A; Leitner, W; Pfaltz, A

Publication Date:: Wed Jul 14 00:00:00 EDT 1999

Research Org.:: Max-Planck-Inst. fur Kohlenforschung, Muelheim/Ruhr (DE)

OSTI Identifier:: 20000106

Resource Type:: Journal Article

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Volume: 121; Journal Issue: 27; Other Information: PBD: 14 Jul 1999; Journal ID: ISSN 0002-7863

Country of Publication:: United States

Language:: English

Subject:: 32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION; IRIDIUM; SUPERCRITICAL GAS EXTRACTION; CARBON DIOXIDE; HYDROGENATION; IMINES; CATALYSIS; STEREOCHEMISTRY

Citation Formats


                    Kainz, S, Brinkmann, A, Leitner, W, and Pfaltz, A. Iridium-catalyzed enantioselective hydrogenation of imines in supercritical carbon dioxide.  United States: N. p., 1999. 
        Web.  doi:10.1021/ja984309i.

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                    Kainz, S, Brinkmann, A, Leitner, W, & Pfaltz, A. Iridium-catalyzed enantioselective hydrogenation of imines in supercritical carbon dioxide.  United States.  https://doi.org/10.1021/ja984309i

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                    Kainz, S, Brinkmann, A, Leitner, W, and Pfaltz, A. 1999.  
        "Iridium-catalyzed enantioselective hydrogenation of imines in supercritical carbon dioxide".  United States.  https://doi.org/10.1021/ja984309i.

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@article{osti_20000106,

  title        = {Iridium-catalyzed enantioselective hydrogenation of imines in supercritical carbon dioxide},

  author       = {Kainz, S and Brinkmann, A and Leitner, W and Pfaltz, A},

  abstractNote = {Supercritical carbon dioxide (scCO{sub 2}) was shown to be a reaction medium with unique properties for highly efficient iridium-catalyzed enantioselective hydrogenation of prochiral imines. Cationic iridium(I) complexes with chiral phosphinodihydrooxazoles, modified with perfluoroalkyl groups in the ligand or in the anion, were synthesized and tested in the hydrogenation of N-(1-phenylethylidene)aniline. Both the side chains and the lipophilic anions increased the solubility, but the choice of the anion also had a dramatic effect on the enantioselectivity with tetrakis-3,5-bis(trifluoromethyl)phenylborate (BARF) leading to the highest asymmetric induction. (R)-N-phenyl-1-phenylethylamine was formed quantitatively within 1 h in scCO{sub 2}[d(CO{sub 2}) = 0.75 g mL{sup {minus}1}] at 40 C and a H{sub 2} pressure of 30 bar with enantiomeric excesses of up to 81% using 0.078 mol % catalyst. The use of scCO{sub 2} instead of conventional solvents such as CH{sub 2}Cl{sub 2} allowed the catalyst loading to be lowered significantly owing to a change in the rate profile of the reaction. the homogeneous nature of the catalytically active species under the reaction conditions was demonstrated and was found to depend strongly on the composition of the reaction mixture and especially on the presence of the substrate. Utilizing the selective extractive properties of scCO{sub 2}, the product could be readily separated from the catalyst, which could be recycled several times without significant loss of activity and enantioselectivity. High-pressure FT-IR and NMR investigations revealed that the reactivity of the products to form the corresponding carbamic acids plays an important role for the application of this new methodology.},

  doi          = {10.1021/ja984309i},

  url          = {https://www.osti.gov/biblio/20000106},
  journal      = {Journal of the American Chemical Society},

  issn         = {0002-7863},

  number       = 27,

  volume       = 121,

  place        = {United States},

  year         = {Wed Jul 14 00:00:00 EDT 1999},

  month        = {Wed Jul 14 00:00:00 EDT 1999}

}

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