A series of 2-deoxy-glycopyranosyl cyanides with d-arabino, d-lyxo, d-erythro, and d-threo configurations was synthesized from the corresponding glycals via 2-deoxy-glycopyranosyl acetates. The cyanides were transformed to anhydro-aldose tosylhydrazones by reduction with NaH2PO2/Ra-Ni in the presence of tosylhydrazine. The tosylhydrazones furnished 2-deoxy-exo-glycals under modified Bamford-Stevens conditions. Photoinitiated thiol-ene additions of these exo-glycals resulted in the corresponding C-(2-deoxy-d-glycopyranosyl)methyl sulfides in medium to good yields with exclusive regio- and stereoselectivities in most cases. Several disaccharide mimics with a C-S moiety in place of the glycosidic oxygen were also obtained.
ASJC Scopus subject areas
- Materials Chemistry