Abstract: The reactions between substituted phenylmagnesium bromides and α-D-tetra-acetyl-glucopyranosyl halides were studied. 4-methoxy phenylmagnesium bromides gave mainly β-C-glucoside.In the case of 2-methoxy-phenylmagnesium bromide,four products were obtained. They were l-α-(2-methoxy phenyl)-2,3,4,6-D-tetraace-tyl glucopyranoside, 1-β-(2-methoxy phenyl)-D-triacetyl-glucopyranoside, D-tetra-acetylglucopyranose,and l-deoxy-2-(2-methoxy phenyl)-2,3,4,6-D-tetraacetylglu-copyranoside. 2, 4-dimethoxyphenylmagncsium bromide, both α-and β-C-glucosides were separated. In the cases of 2-benzyloxy and 2,6-dibenzyloxy phenylmagne-sium bromides, the steric effect of the bulky substituents at ortho position prevented normol coupling reaction.