Anomeric α-azido acid (2-azido-2-deoxy-hept-2-ulopyranosonic acid) derivatives en route to peptides incorporating sugar amino acids

K. Czifrák, Péter Szilágyi, L. Somsák

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

Per-O-acylated 2,6-anhydro-aldoheptonic acids of d-glycero-d-gulo and d-glycero-l-manno configuration obtained by nitrosation of the corresponding aldonamides were transformed into methyl-, tert-butyl-, 2,2,2-trichloroethyl-, and pentachlorophenyl esters, acid chlorides and glycinamides by standard procedures. Radical-mediated bromination either by bromine in boiling CHCl 3 under illumination, or NBS in refluxing CCl4 in the presence of Bz2O2 or AIBN, or Na2S 2O4-KBrO3 in CH2Cl2-water biphasic solvent mixture at rt gave axial anomers of the 2-bromides of the above esters and acid chlorides (2-bromo-2-deoxy-α-d-hept-2-ulopyranosonic acid derivatives), while a glycinamide was split along the -H2C-NH- bond. Anomeric bromides of the glycinamides were obtained by N-acylation of a glycine ester with the pentachlorophenyl 2-bromo-2-deoxy-ulosonates. In this reaction the axial anomeric bromide proved stable. Sodium azide in DMSO or DMF was used for the substitution of the anomeric bromides. These reactions proceeded with inversion in the case of each ester and glycinamide to produce equatorial azides (2-azido-2-deoxy-β-d-hept-2-ulopyranosonic acid derivatives). The azide substitution in 2-bromo-2-deoxy-α-d-galacto-hept- 2-ulopyranosonic acid chloride gave 2-azido-2-deoxy-α-d-galacto-hept-2- ulopyranosonic acid azide with retention of the anomeric configuration. This acid azide was coupled with a glycine ester to give an axial anomeric azide. These transformations represent highly stereoselective routes to both anomers of dipeptides incorporating anomeric α-azido acids.

Original languageEnglish
Pages (from-to)127-141
Number of pages15
JournalTetrahedron Asymmetry
Volume16
Issue number1
DOIs
Publication statusPublished - Jan 10 2005

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Sugar Acids
sugars
Sugars
Peptides
peptides
amino acids
Amino acids
routes
Derivatives
Azides
Amino Acids
acids
Acids
esters
Esters
Bromides
bromides
Chlorides
chlorides
glycine

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry
  • Materials Chemistry
  • Drug Discovery

Cite this

Anomeric α-azido acid (2-azido-2-deoxy-hept-2-ulopyranosonic acid) derivatives en route to peptides incorporating sugar amino acids. / Czifrák, K.; Szilágyi, Péter; Somsák, L.

In: Tetrahedron Asymmetry, Vol. 16, No. 1, 10.01.2005, p. 127-141.

Research output: Contribution to journalArticle

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N2 - Per-O-acylated 2,6-anhydro-aldoheptonic acids of d-glycero-d-gulo and d-glycero-l-manno configuration obtained by nitrosation of the corresponding aldonamides were transformed into methyl-, tert-butyl-, 2,2,2-trichloroethyl-, and pentachlorophenyl esters, acid chlorides and glycinamides by standard procedures. Radical-mediated bromination either by bromine in boiling CHCl 3 under illumination, or NBS in refluxing CCl4 in the presence of Bz2O2 or AIBN, or Na2S 2O4-KBrO3 in CH2Cl2-water biphasic solvent mixture at rt gave axial anomers of the 2-bromides of the above esters and acid chlorides (2-bromo-2-deoxy-α-d-hept-2-ulopyranosonic acid derivatives), while a glycinamide was split along the -H2C-NH- bond. Anomeric bromides of the glycinamides were obtained by N-acylation of a glycine ester with the pentachlorophenyl 2-bromo-2-deoxy-ulosonates. In this reaction the axial anomeric bromide proved stable. Sodium azide in DMSO or DMF was used for the substitution of the anomeric bromides. These reactions proceeded with inversion in the case of each ester and glycinamide to produce equatorial azides (2-azido-2-deoxy-β-d-hept-2-ulopyranosonic acid derivatives). The azide substitution in 2-bromo-2-deoxy-α-d-galacto-hept- 2-ulopyranosonic acid chloride gave 2-azido-2-deoxy-α-d-galacto-hept-2- ulopyranosonic acid azide with retention of the anomeric configuration. This acid azide was coupled with a glycine ester to give an axial anomeric azide. These transformations represent highly stereoselective routes to both anomers of dipeptides incorporating anomeric α-azido acids.

AB - Per-O-acylated 2,6-anhydro-aldoheptonic acids of d-glycero-d-gulo and d-glycero-l-manno configuration obtained by nitrosation of the corresponding aldonamides were transformed into methyl-, tert-butyl-, 2,2,2-trichloroethyl-, and pentachlorophenyl esters, acid chlorides and glycinamides by standard procedures. Radical-mediated bromination either by bromine in boiling CHCl 3 under illumination, or NBS in refluxing CCl4 in the presence of Bz2O2 or AIBN, or Na2S 2O4-KBrO3 in CH2Cl2-water biphasic solvent mixture at rt gave axial anomers of the 2-bromides of the above esters and acid chlorides (2-bromo-2-deoxy-α-d-hept-2-ulopyranosonic acid derivatives), while a glycinamide was split along the -H2C-NH- bond. Anomeric bromides of the glycinamides were obtained by N-acylation of a glycine ester with the pentachlorophenyl 2-bromo-2-deoxy-ulosonates. In this reaction the axial anomeric bromide proved stable. Sodium azide in DMSO or DMF was used for the substitution of the anomeric bromides. These reactions proceeded with inversion in the case of each ester and glycinamide to produce equatorial azides (2-azido-2-deoxy-β-d-hept-2-ulopyranosonic acid derivatives). The azide substitution in 2-bromo-2-deoxy-α-d-galacto-hept- 2-ulopyranosonic acid chloride gave 2-azido-2-deoxy-α-d-galacto-hept-2- ulopyranosonic acid azide with retention of the anomeric configuration. This acid azide was coupled with a glycine ester to give an axial anomeric azide. These transformations represent highly stereoselective routes to both anomers of dipeptides incorporating anomeric α-azido acids.

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