Large scale enantiomeric synthesis, purification, and characterization of ω-unsaturated amino acids via a Gly-Ni(II)-BPB-complex

Xuyuan Gu, John M. Ndungu, Wei Qiu, Jinfa Ying, Michael D. Carducci, Hank Wooden, Victor J Hruby

Research output: Contribution to journalArticle

31 Citations (Scopus)

Abstract

The enantiomeric syntheses of ω-unsaturated amino acids and β-substituted ω-unsaturated amino acids were accomplished by using Gly-Ni-2[N-(N′-benzylprolyl)amino]benzophenone (BPB) as a chiral auxiliary. The synthesis provides excellent yields and high diastereoselectivities. The product crystallization followed by isomer epimerization strategy makes the reaction practical and useful for large-scale preparations. Dialkylation of the Ni(II)-complex, which was designed for mechanistic considerations, revealed that high diastereoselectivity is obtained due to the thermodynamic conformational stability of the Ni(II)-complex. The assignment of absolute configuration was accomplished by NMR, which is supported by corresponding X-ray structure and optical rotation data. Both enantiomerically pure amino acids can be synthesized in this alkylation-hydrolysis two-step strategy in multi gram scales.

Original languageEnglish (US)
Pages (from-to)8233-8243
Number of pages11
JournalTetrahedron
Volume60
Issue number37
DOIs
StatePublished - Sep 6 2004

Fingerprint

Purification
Amino Acids
Optical rotation
Optical Rotation
Alkylation
Crystallization
Thermodynamics
Isomers
Hydrolysis
Thermodynamic stability
Nuclear magnetic resonance
X-Rays
X rays
benzophenone

Keywords

  • Alkylation
  • Amino acids
  • Diastereoselectivity
  • Epimerization
  • Ni(II)-complex chiral auxiliary

ASJC Scopus subject areas

  • Biochemistry
  • Organic Chemistry
  • Drug Discovery

Cite this

Large scale enantiomeric synthesis, purification, and characterization of ω-unsaturated amino acids via a Gly-Ni(II)-BPB-complex. / Gu, Xuyuan; Ndungu, John M.; Qiu, Wei; Ying, Jinfa; Carducci, Michael D.; Wooden, Hank; Hruby, Victor J.

In: Tetrahedron, Vol. 60, No. 37, 06.09.2004, p. 8233-8243.

Research output: Contribution to journalArticle

Gu, Xuyuan ; Ndungu, John M. ; Qiu, Wei ; Ying, Jinfa ; Carducci, Michael D. ; Wooden, Hank ; Hruby, Victor J. / Large scale enantiomeric synthesis, purification, and characterization of ω-unsaturated amino acids via a Gly-Ni(II)-BPB-complex. In: Tetrahedron. 2004 ; Vol. 60, No. 37. pp. 8233-8243.
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AU - Carducci, Michael D.

AU - Wooden, Hank

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