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Abstract C-Alkyl glycosides represent an attractive class of nonhydrolyzable carbohydrate mimetics which possess enormous potential as next-generation therapeutics. Methods for the direct stereoselective synthesis of C-alkyl glycosides with a broad substrate tolerance are limited, however. This is especially in the case of β-linked C-alkyl glycosides, where direct methods for synthesis from commonly available coupling partners remain limited. This Account describes the evolution of our laboratory’s studies on glycosyl sulfonate chemistry from a method for the construction of simple β-linked 2-deoxy-sugars to a technology for the direct synthesis of β-linked acyl and homoacyl glycosides that can be elaborated into more complex structures. 1 Introduction 2 Glycosyl Sulfonates 3 Glycosyl Sulfonates in Oligosaccharide Synthesis 4 Matching Donor and Sulfonate Reactivity 5 β-Linked C-Acyl and Homoacyl Glycoside Synthesis 6 Elaboration to other Products 7 Conclusion
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Glycosyl Sulfonates Beyond Triflates
Abstract While glycosyl triflates are frequently invoked as intermediates in many chemical glycosylation reactions, the chemistry of other glycosyl sulfonates remains comparatively underexplored. Given the reactivity of sulfonates can span several orders of magnitude, this represents an untapped resource for the development of stereoselective glycosylation reactions. This personal account describes our laboratories efforts to take advantage of this reactivity to develop β‐specific glycosylation reactions. Initial investigations led to the development of 2‐deoxy‐sugar tosylates as highly selective donors for β‐glycoside synthesis, an approach which has been used to great success by our group and others for the construction of deoxy‐sugar oligosaccharides and natural products. Subsequent studies demonstrate that “matching” the reactivity of the sulfonate to that of the sugar donor leads to highly selective SN2‐glycosylations with a range of substrates.
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- Award ID(s):
- 1954841
- PAR ID:
- 10303415
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- The Chemical Record
- Volume:
- 21
- Issue:
- 11
- ISSN:
- 1527-8999
- Page Range / eLocation ID:
- p. 3102-3111
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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