Metathesis of structurally preorganized bivalent carbohydrates. Synthesis of macrocyclic and oligomeric scaffolds

Organic Letters

Volumn 6, Issue 22, 2004, Pages 3961-3964

  Velasco Torrijos, Trinidad ^a   Murphy, Paul V ^a  

^a UNIVERSITY COLLEGE DUBLIN   (Ireland)

Author keywords

[No Author keywords available]

Indexed keywords

CARBOHYDRATE;

ARTICLE; CHEMICAL REACTION; MOLECULAR MODEL; OLIGOMERIZATION; SYNTHESIS; X RAY CRYSTALLOGRAPHY;

CARBOHYDRATES; CATALYSIS; CRYSTALLOGRAPHY, X-RAY; CYCLIZATION; DIAMINES; GLUCURONIC ACID; LIGANDS; MOLECULAR MIMICRY; OLIGOPEPTIDES; PEPTIDES, CYCLIC; PROTEIN STRUCTURE, SECONDARY; STEREOISOMERISM;

EID: 8744229693     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0484254     Document Type: Article

References (31)

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7. Tosin, M.; Müller-Bunz, H.; Murphy, P. V. Chem. Commun. 2004, 494.
8. The Z-hydrogen-bonded and Z-anti conformations (Figure 1) have been observed for such secondary amides in X-ray crystal structures. Tosin, M.; O'Brien, C.; Murphy, P. V. Private communication.
9. The U-shaped or cis or syn conformation is defined as the carbohydrate groups being on same side of plane defined by aromatic ring; the S-shaped or trans or anti conformation have the carbohydrates on opposite sides of the ring.
10. 1H NMR spectrum for 2 shows two signal sets due to amide bond rotamers: the first set (major structural isomer) is assigned to 2a and/ or 2b; the second set is assigned to isomer 2c or a related syn conformer (not shown).
11. For an example of conformationally unbiased macrocyclisation by RCM, see: Fürstner, A.; Langemann, K. J. Org. Chem. 1996, 61, 3942.
12. For a review of application of metathesis in glycobiology, see: Leeuwenburgh, M. A.; van der Marel, G. A.; Overkleeft, H. S. Curr. Opin. Chem. Biol. 2003, 7, 757.
13. (a) Tosin, M.; Murphy, P. V. Org. Lett., 2002, 4, 3675-78.
14. (b) Poláková, M.; Pitt, N.; Tosin, M.; Murphy, P. V. Angew. Chem., Int. Ed. 2004, 43, 2518.
15. The origin of the stereoselectivity from 4 and related donors is currently being investigated. Murphy, P. V.; Poláková, M.; Pitt, N.; Tosin, M. 22nd International Carbohydrate Symposium, Glasgow, UK, July 23rd-27, 2004, C44.
16. The TES ether was prepared as it has a higher boiling point than the TMS ether which simplified isolation and purification.
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19. 2. The analytical data for the reduced products is provided in the Supporting Information.
20. Cross metathesis followed by ring-closing metathesis has been observed previously. Smith, A. B.; Adams, C. M.; Kozmin, S. A.; Paone, D. V. J. Am. Chem. Soc. 2001, 123, 5925.
21. The 2D NOE spectrum of 8 showed a strong cross-peak between the signal for aromatic protons and that of the H-5 proton of the glucuronic acid residue but not between H-5 and the methyl group, consistent with a preferred E-anti conformation for amides of 8.
22. For a previous example of copper promoted preorganization of olefins for RCM, see: Weck, M.; Mohr, B.; Sauvage, J.-P.; Grubbs, R. H. J. Org. Chem. 1999, 64, 5463.
23. The alkenes were separated by HPLC.
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25. Low energy structures were obtained by a conformational search with Macromodel 8.5. All low energy structures within 20 kJ/mol of the global minimum were retained. Only E-anti conformers with the U-shaped structure were found and this included isomers with the alkene either parallel or perpendicular to the aromatic ring. The coordinates for low energy structures are provided as Macromodel dat files as Supporting Information.
26. 2O. The signals were first assigned with standard Varian gradient COSY experiments at 25°C. A two-dimensional Tr-ROESY experiment (spin-lock field of 2.2 kHz with mixing time of 0.5 s, at 30°C) was used to obtain the 2D ROESY spectrum.
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