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. 2019 May 20;58(21):6957-6961.
doi: 10.1002/anie.201901346. Epub 2019 Apr 9.

Phenanthroline-Catalyzed Stereoretentive Glycosylations

Fei Yu  1 , Jiayi Li  1 , Paul M DeMent  1 , Yi-Jung Tu  1 , H Bernhard Schlegel  1 , Hien M Nguyen  1
Affiliations

Phenanthroline-Catalyzed Stereoretentive Glycosylations

Fei Yu et al. Angew Chem Int Ed Engl. .

Abstract

Carbohydrates are essential moieties of many bioactive molecules in nature. However, efforts to elucidate their modes of action are often impeded by limitations in synthetic access to well-defined oligosaccharides. Most of the current methods rely on the design of specialized coupling partners to control selectivity during the formation of glycosidic bonds. Reported herein is the use of a commercially available phenanthroline to catalyze stereoretentive glycosylation with glycosyl bromides. The method provides efficient access to α-1,2-cis glycosides. This protocol has been performed for the large-scale synthesis of an octasaccharide adjuvant. Density-functional theory calculations, together with kinetic studies, suggest that the reaction proceeds by a double SN 2 mechanism.

Keywords: glycosylation; oligosaccharides; organocatalysis; reaction mechanisms; stereoselectivity.

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Conflict of interest statement

Conflict of interest

The authors declare no conflict of interest.

Figures

Figure 1.
Figure 1.
Mechanistic studies.
Scheme 1.
Scheme 1.
Introduction and synopsis of current work
Scheme 2.
Scheme 2.
Synthesis of octasaccharide 40. [a] 5 – 15 mol% of 4, IBO (2 equiv.), MTBE (2 M), 50 oC, 24 h, 34: 89%, α:β > 20:1; 37: 86%, α:β > 20:1; 40: 77%, α:β > 20:1. [b] NaOMe, MeOH, CH2Cl2, 25 oC, 35: 99%, 38: 70%. [c] PTSA, Ac2O, 70 oC, 2 h (glycosyl acetates: 36S: 61%, 39S: 51%, see SI); then HBr/AcOH, CH2Cl2, 0 oC, 15 min, and 36 and 39 were used in the next step without further purification.
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