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Synthesis of non-proteinogenic (D)- or (L)-amino acids by asymmetric hydrogenation

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Summary

Non-proteinogenic amino acids play an increasing role in oligopeptide chemistry. Their pharmacological and chemical properties, caused by D-configuration and “unnatural” residues, are more and more used for drug design. Different methods of asymmetric synthesis have been developed during the last decade to prepare “unusual” amino acids. One of them, the asymmetric hydrogenation of dehydroamino aids catalyzed by chiral rhodium (I) complexes, will be described. A series of examples, D- and L-configured, like naphthyl-, thienyl-, furyl-, and pyridylalanines, as well as phenylalanines substituted by chlorine, fluorine, p-nitro, p-methyl, p-trifluoromethyl, p-isopropyl, and p-tert-butyl have been prepared and characterized. Some analytical data like melting points and values of optical rotation are summarized in tables.

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Abbreviations

(−)-DIOP:

(4R,5R)-4,5-Bis(diphenylphosphinomethyl)-2,2-dimethyl-1,3-dioxolane

(−)-BPPM:

(2S,4S)-N-tert-Butoxycarbonyl-4-diphenylphosphino-2-diphenylphosphinomethyl-pyrrolidine

Ph-β-glup:

Phenyl 4,6-O-(R)-benzylidene-2,3-O-bis(diphenylphosphino)-β-D-glucopyranoside

DuPHOS:

1,2-bis-(phospholano)benzene

PROPRAPHOS:

2,3-O,N-bis(diphenylphosphino)-1-(naphthoxy)-2-hydroxy-3-isopropylamino propane

PINDOPHOS:

2,3-O,N-bis(diphenylphosphino)-1-(4-indolyloxy)-2-hydroxy-3-isopropylamino propane

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Authors and Affiliations

  1. Institut für Organische Katalyseforschung an der Universität Rostock e.V., Buchbinderstraße 5-6, D-18055, Rostock, Germany

    H. J. Kreuzfeld, Chr Döbler, U. Schmidt & H. W. Krause

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  1. H. J. Kreuzfeld
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  2. Chr Döbler
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  3. U. Schmidt
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  4. H. W. Krause
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Kreuzfeld, H.J., Döbler, C., Schmidt, U. et al. Synthesis of non-proteinogenic (D)- or (L)-amino acids by asymmetric hydrogenation. Amino Acids 11, 269–282 (1996). https://doi.org/10.1007/BF00807936

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