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. 2015 May 1;6(5):2687-2704.
doi: 10.1039/C5SC00280J.

Stereocontrolled 1,2- cis glycosylation as the driving force of progress in synthetic carbohydrate chemistry

Swati S Nigudkar  1 , Alexei V Demchenko  1
Affiliations

Stereocontrolled 1,2- cis glycosylation as the driving force of progress in synthetic carbohydrate chemistry

Swati S Nigudkar et al. Chem Sci. .

Abstract

Recent developments in stereoselective 1,2-cis glycosylation that have emerged during the past decade are surveyed herein. For detailed coverage of the previous achievements in the field the reader is referred to our earlier reviews: A. V. Demchenko, Curr. Org. Chem., 2003, 7, 35–79 and Synlett, 2003, 1225–1240.

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Figures

Fig. 1
Fig. 1. Common monosaccharide residues found in the mammalian and bacterial glycome.
Fig. 2
Fig. 2. Naturally occurring oligosaccharides containing 1,2-cis linkages.
Scheme 1
Scheme 1. General outline of glycosylation and the key intermediates involved.
Fig. 3
Fig. 3. Factors affecting stereoselectivity.
Scheme 2
Scheme 2. Stereoselective glycosylation with ethyl (R)- and (S)-mandelate protected glycosyl donor 1.
Scheme 3
Scheme 3. Synthesis of C-2 (S)-phenyl-thiomethylbenzyl ether-protected glycosyl donor 6 and its glycosidation.
Scheme 4
Scheme 4. Stereoselective glycosylation via sulfonium ions.
Scheme 5
Scheme 5. Rationalization of the high β-selectivity achieved with 2-azidomannouronate donor 37.
Scheme 6
Scheme 6. HAD synthesis of β-mannan and α-glucan.
Scheme 7
Scheme 7. β-Linked mannans by the sulfoxide protocol.
Scheme 8
Scheme 8. Selective α-glycosylation with N-acetyl- and N-benzyl-2,3-oxazolidinone-protected donors 67 and 70.
Scheme 9
Scheme 9. Acyl groups in acceptors enhance stereoselectivity.
Scheme 10
Scheme 10. Effect of the reaction solvent.
Scheme 11
Scheme 11. The solvent effect on preactivation-based glycosylation.
Scheme 12
Scheme 12. Solvent and temperature effects.
Scheme 13
Scheme 13. DMF-mediated glycosylation.
Scheme 14
Scheme 14. DMF-mediated synthesis of trisaccharide 105.
Scheme 15
Scheme 15. Stereoselective glycosidation of superdisarmed thioglycoside 106 via reactive β-bromide intermediate.
Scheme 16
Scheme 16. Synthesis of 1,2-cis-linked glycosides by activation of thioglycosides in the presence of TBAI.
Scheme 17
Scheme 17. Effect of metal complexation on the stereoselectivity of glycosylation.
Scheme 18
Scheme 18. β-Mannosylation via NAP-tether mediated IAD.
Scheme 19
Scheme 19. Automated synthesis of Globo H hexasaccharide.
Scheme 20
Scheme 20. Glycosylation on an ionic liquid support.
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