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Volumn 49, Issue 43, 2010, Pages 7955-7957

Isomerization-induced asymmetric coordination chemistry: From auxiliary control to asymmetric catalysis

Author keywords

Asymmetric catalysis; Auxiliary control; Chirality; Coordination chemistry; Ruthenium

Indexed keywords

ASYMMETRIC CATALYSIS; AUXILIARY CONTROL; BIPYRIDINE LIGANDS; COORDINATION CHEMISTRY; ELECTRON-RICH; METHOXY; OCTAHEDRAL COORDINATION; RUTHENIUM COMPLEXES; TRANS-CIS ISOMERIZATION;

EID: 78349273626     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201003139     Document Type: Article
Times cited : (46)

References (25)
  • 1
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    • For asymmetric coordination chemistry, see
    • For asymmetric coordination chemistry, see
  • 6
    • 75249106896 scopus 로고    scopus 로고
    • For a recent review on chiral-auxiliary-mediated asymmetric coordination chemistry, see:, - 758
    • For a recent review on chiral-auxiliary-mediated asymmetric coordination chemistry, see:, E. Meggers, Chem. Eur. J. 2010, 16, 752 - 758.
    • (2010) Chem. Eur. J. , vol.16 , pp. 752
    • Meggers, E.1
  • 7
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    • Synthesized in analogy to:, - 332
    • Synthesized in analogy to:, J. L. Walsh, B. Durham, Inorg. Chem. 1982, 21, 329 - 332.
    • (1982) Inorg. Chem. , vol.21 , pp. 329
    • Walsh, J.L.1    Durham, B.2
  • 9
    • 33751392007 scopus 로고
    • The ee of (S)- SO was ≥99%. Obtained conveniently from optically pure sulfinates of diacetone glucose. For the method, see:, - 6796
    • The ee of (S)- SO was ≥99%. Obtained conveniently from optically pure sulfinates of diacetone glucose. For the method, see:, I. Fernádez, N. Khiar, J. M. Llera, F. Alcudia, J. Org. Chem. 1992, 57, 6789 - 6796.
    • (1992) J. Org. Chem. , vol.57 , pp. 6789
    • Fernádez, I.1    Khiar, N.2    Llera, J.M.3    Alcudia, F.4
  • 10
    • 78349288825 scopus 로고    scopus 로고
    • The reaction of a chiral monodentate sulfoxide with a related trans complex leads to only very modest diastereoselectivities
    • The reaction of a chiral monodentate sulfoxide with a related trans complex leads to only very modest diastereoselectivities; see
  • 13
    • 33748500423 scopus 로고    scopus 로고
    • The structure also reveals a close intramolecular contact (3.12Aα) between the sulfoxide oxygen and the CH group next to N3, which could be interpreted with a weak S-O⋯H-C hydrogen bond. For an analogous interaction, see:, - 3709
    • The structure also reveals a close intramolecular contact (3.12Aα) between the sulfoxide oxygen and the CH group next to N3, which could be interpreted with a weak S-O⋯H-C hydrogen bond. For an analogous interaction, see:, D. Hesek, Y. Inoue, S. R. L. Everitt, H. Ishida, M. Kunieda, M. G. B. Drew, J. Chem. Soc. Dalton Trans. 1999, 3701 - 3709.
    • (1999) J. Chem. Soc. Dalton Trans. , pp. 3701
    • Hesek, D.1    Inoue, Y.2    Everitt, S.R.L.3    Ishida, H.4    Kunieda, M.5    Drew, M.G.B.6
  • 14
    • 78349291122 scopus 로고    scopus 로고
    • This is consistent with the observed high chemical instability of the minor diastereomer Λ-(R)- 2
    • This is consistent with the observed high chemical instability of the minor diastereomer Λ-(R)- 2.
  • 15
    • 0033800719 scopus 로고    scopus 로고
    • For structural and kinetic trans effects in octahedral complexes, see:, 5- 80
    • For structural and kinetic trans effects in octahedral complexes, see:, B. J. Coe, S. J. Glenwright, Coord. Chem. Rev. 2000, 203, 5- 80.
    • (2000) Coord. Chem. Rev. , pp. 203
    • Coe, B.J.1    Glenwright, S.J.2
  • 16
    • 78349285506 scopus 로고    scopus 로고
    • Optimized reaction conditions: 50 m M Δ-(S)- 2, 15 equiv bpy, 5 equiv TFA, distilled and dry MeCN, 110 C in a sealed brown-glass vial, 2 h. See the Supporting Information for more details
    • Optimized reaction conditions: 50 m M Δ-(S)- 2, 15 equiv bpy, 5 equiv TFA, distilled and dry MeCN, 110 C in a sealed brown-glass vial, 2 h. See the Supporting Information for more details.
  • 17
    • 78349285901 scopus 로고    scopus 로고
    • For ligand substitutions under retention of the metal-centered configuration
    • For ligand substitutions under retention of the metal-centered configuration, see
  • 23
    • 78349258891 scopus 로고    scopus 로고
    • Optimized reaction conditions for the asymmetric catalysis with chiral sulfoxides: 300 m M 1, 0.2 equiv (S)- SO or (S)- SO′, 1.0 equiv bpy, 6.0 equiv TFA, ethylene glycol, 95 C in a sealed brown-glass vial under air, 48 h; thereafter addition of 10 equiv bpy and another 2 h at 95 C to replace the ruthenium-bound catalyst. See the Supporting Information for more details
    • Optimized reaction conditions for the asymmetric catalysis with chiral sulfoxides: 300 m M 1, 0.2 equiv (S)- SO or (S)- SO′, 1.0 equiv bpy, 6.0 equiv TFA, ethylene glycol, 95 C in a sealed brown-glass vial under air, 48 h; thereafter addition of 10 equiv bpy and another 2 h at 95 C to replace the ruthenium-bound catalyst. See the Supporting Information for more details.
  • 24
    • 78349233079 scopus 로고    scopus 로고
    • The chiral sulfoxides are configurationally stable under the acidic reaction conditions
    • The chiral sulfoxides are configurationally stable under the acidic reaction conditions.
  • 25
    • 78349286945 scopus 로고    scopus 로고
    • The ruthenium complex intermediates and products were tested to be configurationally stable and soluble under the applied reactions conditions, which excludes mechanistic explanations for the observed enantiomeric excess involving chiral ion-pairing interactions or solubility differences of the intermediate ruthenium diastereomers
    • The ruthenium complex intermediates and products were tested to be configurationally stable and soluble under the applied reactions conditions, which excludes mechanistic explanations for the observed enantiomeric excess involving chiral ion-pairing interactions or solubility differences of the intermediate ruthenium diastereomers.


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