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Synlett 2015; 26(16): 2267-2271
DOI: 10.1055/s-0035-1560172
DOI: 10.1055/s-0035-1560172
letter
Novel Benzyl-Free Glycosyl Donors for Highly Stereoselective 1,2-cis-Fucosylation
Weitere Informationen
Publikationsverlauf
Received: 27. April 2015
Accepted after revision: 21. Juli 2015
Publikationsdatum:
02. September 2015 (online)
![](https://www.thieme-connect.de/media/synlett/201516/lookinside/thumbnails/st-2015-d0318-l_10-1055_s-0035-1560172-1.jpg)
Dedicated to the memory of Professor Nikolay K. Kochetkov (1915–2005)
Abstract
Novel glycosyl donors with a triisopropylsilyl (TIPS) nonparticipating group at O-2 were introduced for use in 1,2-cis-fucosylation. Coupling of 2-O-TIPS-substituted thiofucosyl donors with N-trifluoroacetyl-β-d-glucosamine mono- and disaccharide derivatives was found to lead exclusively to α-linked oligosaccharides. No remote participation in 2-O-TIPS thiofucosyl donors seems to be required to favor α-selective fucosylation.
Key words
glycosylation - stereoselectivity - protecting groups - neighboring-group effects - substituent effectsSupporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0035-1560172 and contains detailed experimental procedures, NMR and high-resolution ESI mass spectrometry data for all target compounds and key intermediates.
- Supporting Information
-
References and Notes
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- 30 Comparison of NMR data of 17 with NMR data of the known ethyl 2,3-di-O-acetyl-1-thio-β-l-fucopyranoside31 suggests that some conformational change has occurred in 17 due to the steric bulk of the protecting groups. Analyical Data for 17 1H NMR (300 MHz, C6D6): δ = 1.10–1.22 [m, 24 H, SCH2CH 3, CH(CH3)2], 1.23–1.30 [m, 18 H, CH(CH3)2], 1.32 (d, 3 H, H-6, J = 6.5 Hz), 1.36–1.53 [m, 3 H, CH(CH3)2], 2.22 (d, 1 H, OH, J = 6.0 Hz), 2.53 (dq, 1 H, SCH 2CH3, J = 12.7, 7.5 Hz), 2.68 (dq, 1 H, SCH 2CH3, J = 12.7, 7.4 Hz), 3.41 (qd, 1 H, H-5, J = 6.4, 1.3 Hz), 3.71 (app t, 1 H, H-4, J = 4.2 Hz), 3.88 (dd, 1 H, H-3, J = 7.1, 3.8 Hz), 4.10 (app t, 1 H, H-2, J = 7.3 Hz), 4.47 (d, 1 H, H-1, J = 7.6 Hz). 1H–29Si HMBC correlations: δH = 4.10/δSi = 13.5 [H-2/(i-Pr)3Si], δH = 3.88/δSi = 14.5 [H-3/(i-Pr)3Si].
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For fucosylation in the syntheses of fragments of Lea, see:
For fucosylation in the synthesis of fragments of Lex, see:
For fucosylation in the synthesis of fragments of LexLea, see:
For fucosylation in the synthesis of fragments of glycoprotein N-glycans, see: