Shelf-Stable 3-Thiocresyl-Prop-1-Enyl (TCP) Glycosides in Oligosaccharide Synthesis

Area of Science:

• Carbohydrate Chemistry
• Organic Synthesis
• Glycosylation Strategies

Background:

• Allyl glycosides are common but can lack stability for complex synthesis.
• Developing shelf-stable and reactive glycosyl donors is crucial for efficient oligosaccharide synthesis.

Purpose of the Study:

• To introduce 3-thiocresyl-prop-1-enyl (TCP) glycosides as a stable and active alternative to allyl glycosides.
• To demonstrate the utility of TCP glycosides in synthesizing complex di-, tri-, and oligosaccharides.

Main Methods:

• Transformation of allyl glycosides into TCP glycosides.
• Remote electrophilic activation of TCP glycosides using an iodonium source.
• Synthesis of various pyranosides, furanosides, globo-trioside Gb3 antigen, and oligomannans.
• Mechanistic studies involving thioether and acrolein by-product identification.

Main Results:

• TCP glycosides exhibit remarkable shelf-stability and facile conversion to active glycosyl donors.
• Successful synthesis of diverse oligosaccharides, including biologically relevant structures.
• TCP glycosides function effectively as both glycosyl donors and acceptors.
• Mechanistic studies elucidated the remote activation pathway.

Conclusions:

• TCP glycosides represent a versatile and advantageous platform for oligosaccharide synthesis.
• Their stability, reactivity, and dual functionality offer significant benefits over traditional methods.
• This approach broadens the scope of synthetic carbohydrate chemistry.