Abstract
Intramolecular glycosylation of a glycosyl acceptor temporarily tethered to the 2-hydroxyl group of the glycosyl donor, commonly referred to as Intramolecular Aglycon Delivery (IAD), potentially provides a solution to the perennial problem of how to synthesise 1,2-cis glycosidic linkages with complete stereocontrol. This account summarises developments in this area, focussing on the development within our group of intramolecular glycosylation based on allyl protecting groups (allyl IAD). Optimisation, the current scope and limitations, and further potential developments of allyl IAD are discussed herein.
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1 Introduction
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2 Intramolecular Aglycon Delivery (IAD): Previous Approaches
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2.1 Synthesis of β-Mannosides
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2.2 Synthesis of Other 1,2-cis Glycosides by IAD
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3 NIS-mediated Hindsgaul IAD
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4 Allyl IAD
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4.1 Thioglycoside Donors
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4.2 Glycosyl Fluoride Donors
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4.3 Attempted Facile Synthesis of (1-4) Linked Disaccharides
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4.4 Extension to Other Sugars and Protecting Group Patterns
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4.5 Optimisation
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4.6 Mechanistic Studies
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4.7 Iterative Oligosaccharide Synthesis
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5 Summary and Future Perspectives
Key words
carbohydrates - glycosylations - stereoselective - intramolecular aglycon delivery (IAD) - 1,2-cis-glycosides
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