Transformation of Glycals into 2,3-Unsaturated Glycosyl Derivatives

Ferrier, Robert J.; Zubkov, Oleg A.


Various elimination procedures conducted on appropriate pyranoid and furanoid carbohydrate derivatives, especially on O-protected glycosyl halides afford cyclic vinyl ethers which Fischer (inappropriately) named glycals. These are used extensively in general organic synthesis and for the preparation of non-carbohydrate natural products as well as biologically important complex carbohydrates and glycoconjugates. The best known member, tri-O-acetyl-D-glucal, is normally made from tetra-O-acetyl-alpha-D-glucopyranosyl bromide, is commercially available, and is used very frequently in this chapter to represent the family in examples of the reactions under discussion.

Because of the pronounced region- and stereoselectivities with which their addition reactions can be conducted, glycal derivatives are of major importance in synthesis. They also, however, take part in rearrangement processes that, likewise, have proved useful for synthesis. The principal one involves nucleophilic substitution of the allylic group with allylic rearrangement and results in products having double bonds in the 2, 3 positions and new substituents at the anomeric centers. By far the simplest and most commonly used way to this conversion involves the removal of the allylic substituent of the glycal and the generation of highly resonance-stabilized oxocarbenium ion intermediate. This may then react with nucleophiles at the anomeric center to give products as mixtures of diastereomers. Many examples and variations of this theme are described and form the major part of this chapter, but other ways are also considered

Almost no formal mechanistic studies have been carried out on the reactions in this chapter. Categorization of mechanism required for the treatment of this topic has been done on the basis of conditions used, product identification and largely, chemical intuition.