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Palladium(II)-catalyzed rearrangement of glycal trichloroacetimidates: application to the stereoselective synthesis of glycosyl ureas.
J Am Chem Soc. 2008 Aug 20; 130(33):11210-8.JA

Abstract

The research on the area of glycosyl urea derivatives, in which the O- and N-glycosidic bonds are replaced with the urea-glycosidic linkages, has recently emerged with applications in the field of aminoglycoside antibiotics. We have developed a novel method for the stereoselective synthesis of alpha- and beta-glycosyl ureas via Pd(II)-catalyzed rearrangement of glycal trichloroacetimidates. In our approach, the alpha- and beta-selectivity at the anomeric carbon of N-glycosyl trichloroacetamides depends on the nature of the palladium-ligand catalyst. While the cationic Pd(II)-L-4 (2-trifluoroacetylphenol) complex promotes alpha-selectivity, the neutral Pd(II)-TTMPP-L-5 (4-chloro-2-trifluoroacetylphenol) complex favors beta-selectivity. The resulting alpha- and beta-N-glycosyl trichloroacetamides were further coupled with a diverse array of primary and hindered secondary nitrogen nucleophiles to provide the corresponding glycosyl ureas in moderate to good yields and with no loss of stereochemical integrity at the anomeric carbon. We have further demonstrated the utility of N-glycosyl trichloroacetamides as robust and versatile intermediates in the synthesis of unsymmetrical urea-linked disaccharides and trisaccharide.

Authors+Show Affiliations

Department of Chemistry and Biochemistry, Montana State University, Bozeman, Montana 59717, USA.No affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.

Language

eng

PubMed ID

18642810

Citation

Mercer, Gregory J., et al. "Palladium(II)-catalyzed Rearrangement of Glycal Trichloroacetimidates: Application to the Stereoselective Synthesis of Glycosyl Ureas." Journal of the American Chemical Society, vol. 130, no. 33, 2008, pp. 11210-8.
Mercer GJ, Yang J, McKay MJ, et al. Palladium(II)-catalyzed rearrangement of glycal trichloroacetimidates: application to the stereoselective synthesis of glycosyl ureas. J Am Chem Soc. 2008;130(33):11210-8.
Mercer, G. J., Yang, J., McKay, M. J., & Nguyen, H. M. (2008). Palladium(II)-catalyzed rearrangement of glycal trichloroacetimidates: application to the stereoselective synthesis of glycosyl ureas. Journal of the American Chemical Society, 130(33), 11210-8. https://doi.org/10.1021/ja803378k
Mercer GJ, et al. Palladium(II)-catalyzed Rearrangement of Glycal Trichloroacetimidates: Application to the Stereoselective Synthesis of Glycosyl Ureas. J Am Chem Soc. 2008 Aug 20;130(33):11210-8. PubMed PMID: 18642810.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Palladium(II)-catalyzed rearrangement of glycal trichloroacetimidates: application to the stereoselective synthesis of glycosyl ureas. AU - Mercer,Gregory J, AU - Yang,Jaemoon, AU - McKay,Matthew J, AU - Nguyen,Hien M, Y1 - 2008/07/19/ PY - 2008/7/23/pubmed PY - 2008/10/28/medline PY - 2008/7/23/entrez SP - 11210 EP - 8 JF - Journal of the American Chemical Society JO - J. Am. Chem. Soc. VL - 130 IS - 33 N2 - The research on the area of glycosyl urea derivatives, in which the O- and N-glycosidic bonds are replaced with the urea-glycosidic linkages, has recently emerged with applications in the field of aminoglycoside antibiotics. We have developed a novel method for the stereoselective synthesis of alpha- and beta-glycosyl ureas via Pd(II)-catalyzed rearrangement of glycal trichloroacetimidates. In our approach, the alpha- and beta-selectivity at the anomeric carbon of N-glycosyl trichloroacetamides depends on the nature of the palladium-ligand catalyst. While the cationic Pd(II)-L-4 (2-trifluoroacetylphenol) complex promotes alpha-selectivity, the neutral Pd(II)-TTMPP-L-5 (4-chloro-2-trifluoroacetylphenol) complex favors beta-selectivity. The resulting alpha- and beta-N-glycosyl trichloroacetamides were further coupled with a diverse array of primary and hindered secondary nitrogen nucleophiles to provide the corresponding glycosyl ureas in moderate to good yields and with no loss of stereochemical integrity at the anomeric carbon. We have further demonstrated the utility of N-glycosyl trichloroacetamides as robust and versatile intermediates in the synthesis of unsymmetrical urea-linked disaccharides and trisaccharide. SN - 1520-5126 UR - https://www.unboundmedicine.com/medline/citation/18642810/Palladium_II__catalyzed_rearrangement_of_glycal_trichloroacetimidates:_application_to_the_stereoselective_synthesis_of_glycosyl_ureas_ L2 - https://dx.doi.org/10.1021/ja803378k DB - PRIME DP - Unbound Medicine ER -