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Volumn 8, Issue 22, 2002, Pages 5196-5202

On the enantioselective hydrogenation of isomeric methyl 3-acetamidobutenoates with RhI complexes

Author keywords

Asymmetric synthesis; Hydrogenation; Phosphanes rhodium; amino acids

Indexed keywords

AMINO ACIDS; CATALYSIS; DRUG PRODUCTS; HYDROGENATION; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; SUBSTRATES;

EID: 0037112651     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/1521-3765(20021115)8:22<5196::AID-CHEM5196>3.0.CO;2-P     Document Type: Article
Times cited : (59)

References (58)
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    • In most substrate syntheses the Z isomer is formed predominantly under thermodynamic control, due to hydrogen bonding between amido and carboxyl group.
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    • See also the misleading conclusions derived from the enantioselective hydrogenation of α,β-diaminopropenoic acid: A. J. Robinson, C. Y. Lim, L. He, P. Ma, H.-Y. Li, J. Org. Chem. 2001, 66, 4141-4147.
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    • See also Supporting Information
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    • It should be noted that the remarkable results reported by Gridnev and Imamoto were mainly achieved at very low temperatures, which are in general not usual for enantioselective hydrogenations. Therefore, a change of the mechanism at room temperature and under normal pressure cannot be ruled out. This is also recognized by the authors: "On the other hand, nothing speaks against the possibility of a direct hydrogenation of [the substrate complex]."; ref. [18b]).
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    • See also the ambiguous discussion on the hydrogenation of aacetamido acrylates: K. Rossen, Angew. Chem. 2001, 113, 4747-4749; Angew. Chem. Int. Ed. 2001, 40, 4611-4613.
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    • See also the ambiguous discussion on the hydrogenation of aacetamido acrylates: K. Rossen, Angew. Chem. 2001, 113, 4747-4749; Angew. Chem. Int. Ed. 2001, 40, 4611-4613.
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    • 2 uptake for 5.0 mmol substrate (depicted in Figure 3) is so fast that especially in the initial stage, influence of diffusion cannot be excluded.
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    • note
    • This effect is interpreted by the assumption that intermolecular exchange between diastereomeric substrate-catalyst complexes is "frozen" with decreasing temperature, which can be confirmed by comparison of relevant activation values for the oxidative addition of hydrogen and the retro conversion of the catalyst-substrate complexes into the starting compounds. These effects cause a disturbance in the additional delivery of the more reactive minor complex.
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    • a) D. Heller, H. Buschmann, H.-D. Scharf, Angew. Chem. 1996, 108, 1964-1967; Angew. Chem. Int. Ed. 1996, 35, 1852-1854; Angew. Chem. Int. Ed. 1996, 35, 1852-1854;
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    • a) D. Heller, H. Buschmann, H.-D. Scharf, Angew. Chem. 1996, 108, 1964-1967; Angew. Chem. Int. Ed. 1996, 35, 1852-1854; Angew. Chem. Int. Ed. 1996, 35, 1852-1854;
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    • note
    • For -1 no pressure dependence of the %ee could be observed at 25°C; however the generality of this for other temperatures is doubtful.
  • 56
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    • note
    • Our principle for the measurement for the quantitative investigation of the hydrogenation is based on the recording of the diminution of the volume of the closed reaction system under thermostatted conditions. The atmospheric pressure served as a reference.


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