Abstract
The synthesis of (β-glycosyl1)phenylmethanes by Grignard alkylation of glycosyl halides is investigated. Reaction of tetra-O-acetylglucopyranosyl bromide with benzylmagnesium chloride gave a good yield of a 3:1 mixture of 2-(β-d-glucopyranosyl)toluene and (β-glucosyl)phenylmethane. The requirement for an equatorial 2-acetoxy group and 6-acetoxymethyl group for the formation of the unexpected o-tolyl rearrangement product is explored by using xylosyl, mannosyl, and 2-deoxyglucosyl halides as substrates for the alkylation. Synthesis of (β-glucosyl)phenylmethane by alkylation of 2,3,4,6-tetra-O-benzylglucosyl bromide with benzylmagnesium chloride is also presented.

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