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Volumn 43, Issue 38, 2004, Pages 5066-5069

Enantioselective hydrogenation of β-ketoesters with monodentate ligands

Author keywords

ketoesters; Asymmetric catalysis; Hydrogenation; Ruthenium

Indexed keywords

CATALYSIS; CATALYSTS; HEAT RESISTANCE; HYDROGENATION; RUTHENIUM; TEMPERATURE;

EID: 4944250331     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200460190     Document Type: Article
Times cited : (57)

References (63)
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    • unpublished results
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    • note
    • These ligands are commercially available from Degussa AG/ Catalyst and Initiators.
  • 60
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    • note
    • Importantly, an alternative synthesis of ligand 4a by double metallation of 2,2′-dimethylbinaphthyl with n-butyl lithium in the presence of tetramethylethylenediamine (TMEDA) and direct quenching with commercially available dichlorophenyl-phosphane gave the corresponding ligand with only 80-95% purity (impurities: lithium salts and organic by-products). This decreased purity led to a lower enantioselectivity in the reduction of 5a and the product was obtained with opposite absolute configuration. We do not know currently which impurity is responsible for the different outcome. In this respect, it is also interesting that the addition of lithium and magnesium salts influences the enantioselectivity of the reduction of 5a in the presence of 4a by 5-10%.
  • 61
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    • note
    • We also tried phosphites similar to the Reetz ligand in β-ketoester hydrogenation, but these ligands did not prove to be stable under our conditions (80-120 °C, methanol).
  • 63
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    • note
    • In the case of 5c, dehydrochlorination was observed as a side reaction at higher temperature.


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