||The glycosylation reaction is used in the synthesis of biologically active molecules. The focus of this research concerns the glycosylation reaction of cyclopropyl glycosides and benzenesulfinate glycosides. Cyclopropyl 2,3,4,6-tetra- O -benzyl-[alpha]-D-glycopyranoside and 1-methylcyclopropyl 2,3,4,6-tetra- O -benzyl-[alpha]-D-glycopyranoside were synthesized from vinyl glycoside precursors using the modified Simmons-Smith method and pyridine to precipitate the zinc salt. Glycopeptide formation of N-Fmoc-3- O -(2,3,4,6-Tetra- O -benzyl-[alpha]/[beta]- D-glucohexopyranosyl)-L-serine methyl ester and N-Fmoc- 3- O -(2,3,4,6-Tetra- O -benzyl-[alpha]/[beta]- D-glucohexopyranosyl)-L-threonine methyl ester were accomplished using 1-methylcyclopropyl 2,3,4,6-tetra- O -benzyl-[alpha]- D-glycopyranoside as a glycosyl donor. We also report the direct glycosylation of benzenesulfinic acid and benzenesulfonic acid to glycosides. Benzenesulfinic acid and benzenesulfonic acid in the presence of silver trifluoromethanesulfinate and 1,1,3,3-tetramethylurea were used in the formation of benzenesulfinate and benzenesulfonate glycosides from dibromosugars.