Can Side-Chain Conformation and Glycosylation Selectivity of Hexopyranosyl Donors Be Controlled with a Dummy Ligand?

The use of a phenylthio group (SPh) as a dummy ligand at the 6-position to control the side-chain conformation of a series of hexopyranosyl donors is described. The SPh group limits side-chain conformation in a configuration-specific manner, which parallels that seen in the heptopyranosides, and so influences glycosylation selectivity. With both d- and l-glycero-d-galacto-configured donors, the equatorial products are highly favored as they are with an l-glycero-d-gluco donor. For the d-glycero-d-gluco donor, on the other hand, modest axial selectivity is observed. Selectivity patterns are discussed in terms of the side-chain conformation of the donors in combination with the electron-withdrawing effect of the thioacetal group. After glycosylation, removal of the thiophenyl moiety and hydrogenolytic deprotection is achieved in a single step with Raney nickel.