An unorthodox hydroxymethylation of MEM-protected glucals

During the preparation of 1-tributylstannyl glucals from 1-phenylsulfinyl glycosides an unexpected side reaction was observed for 2,3,4,6-tetra-O-methoxyethoxy (MEM) protected 1-phenylsulfinyl glucoside. Treatment of the latter with lithium diisopropylamide (LDA) afforded the expected, fully MEM protected 1-phenylsulfinyl glucal accompanied by variable amounts of an unexpected 1-phenylsulfinyl 2-hydroxymethyl-3,4,6-tri-O-methoxyethoxyglucal. The amount of the side product rose with increasing concentration of the starting material.