Branched-chain Sugars. VIII. On the Configuration of Branched-chain Sugars from Methyl 3-O-Benzoyl-4,6-O-benzylidene-α-d-arabino-hexopyranosid-2-ulose

Abstract
Stereoselectivities in the Grignard, diazomethane and nitromethane reaction of methyl 3-O-benzoyl-4,6-O-benzylidene-α-d-arabino-hexopyranosid-2-ulose (1) were examined. In contrast to the Grignard reaction of 1 using methylmagnesium iodide to give a single 2-C-methyl derivative (4), the diazomethane reaction followed by reduction afforded another epimer (6). The nitromethan condensation product (10) of 1 was converted into the corresponding 2-C-acetaminomethyl derivative (13). The NMR spectrum of 2-O-acetate of 4 and comparison of the optical rotations of 4, 6, 10 and 13 in cupraramonium solution indicated that 4 and others have d-gluco-and d-manno-configuration, respectively. Discussions were made on the stereoselectivties of these reactions.

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