Asymmetric syntheses via heterocyclic intermediates. 22. Enantioselective synthesis of alpha-alkenyl glycine methyl esters and alphy-alkenyl glycines (beta,gamma-unsaturated amino acids)

Schöllkopf, Ulrich; Nozulak, Joachim; Groth, Ulrich

Asymmetric syntheses via heterocyclic intermediates. 22. Enantioselective synthesis of alpha-alkenyl glycine methyl esters and alphy-alkenyl glycines (beta,gamma-unsaturated amino acids)

Dateien

59_enantioselective.pdfGröße: 1.46 MBDownloads: 696

Datum

1984

Autor:innen

Schöllkopf, Ulrich

Nozulak, Joachim

Groth, Ulrich

Open Access-Veröffentlichung

Open Access Green

Sammlungen

Chemie

Publikationstyp

Zeitschriftenartikel

Publikationsstatus

Published

Erschienen in

Tetrahedron. 1984, 40(8), pp. 1409-1417. ISSN 0040-4020. Available under: doi: 10.1016/S0040-4020(01)82426-1

Zusammenfassung

Enantioselective syntheses of α-alkenyl glycines of type 10 and of type 23 are described that provide these uncommon ammo acids with predictable conf&uration and with ec-values of >95%. Both approaches are based on the bislactim ether method developed by SchBllkopf et al. As for 10: The lithiated his-lactim ether 6 of cyclo(t-val-gly) is reacted with 2-[(dimethyl t-butyl)silyl]alkanals 2 to give the addition products 7 with de> 95%. These on acid hydrolysis afford L-valinate 8 and the methyl (2R)-2-amino4(dimethyl t-butyl)silyl-3-hydroxyalkanoates 9 which are convertible into the (R)-α-alkenyl glycines of type 10. The scope of this synthesis is limited by the fact that the compounds 9 are thermolabile when disubstitued at C-4. As for 23: The lithiated bis-lactim ether 6 is reacted with thioketones 14 to give the addition products 15 with de>95%. The S-methyl compounds 16 undergo elimination to give regioselectively the olefins 18 when treated with Raney-Ni. Alternatively, the olefms 18 are obtained from the sulfonium salts 24 by dimethyl sulfide elimination, although this route is less regiospecific. The compounds 18 are cleaved by dilute hydrochloric acid, liberating L-valinate 8 and (R)-α-alkenyl glycine methvl esters 21. which on further hvdrolvsis vield (R)-α-alkenyl glycines 23. This synthesis is limited only by the availability of thioketones 14.

Fachgebiet (DDC)

540 Chemie

Zitieren

ISO 690

SCHÖLLKOPF, Ulrich, Joachim NOZULAK, Ulrich GROTH, 1984. Asymmetric syntheses via heterocyclic intermediates. 22. Enantioselective synthesis of alpha-alkenyl glycine methyl esters and alphy-alkenyl glycines (beta,gamma-unsaturated amino acids). In: Tetrahedron. 1984, 40(8), pp. 1409-1417. ISSN 0040-4020. Available under: doi: 10.1016/S0040-4020(01)82426-1

BibTex

@article{Schollkopf1984Asymm-9661,
  year={1984},
  doi={10.1016/S0040-4020(01)82426-1},
  title={Asymmetric syntheses via heterocyclic intermediates. 22. Enantioselective synthesis of alpha-alkenyl glycine methyl esters and alphy-alkenyl glycines (beta,gamma-unsaturated amino acids)},
  number={8},
  volume={40},
  issn={0040-4020},
  journal={Tetrahedron},
  pages={1409--1417},
  author={Schöllkopf, Ulrich and Nozulak, Joachim and Groth, Ulrich}
}

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