1,5-Anhydro-2-deoxy-D-hex-1-enitols are versatile synthons’*2. Various functional groups, such as chloro3, fluoro4-7, bromo8, or iodo’-I’, may be introduced at position 2 by either direct or indirect addition of suitable agents across the double bond. Iodination of o-glucal triacetate, using iodine and silver benzoate in dry benzene9*10, iodine and silver acetate in methanol’, N-iodosuccinimide in dry methanol’*, or iodonium bis(2,4,6-trimethylpyridine)perchlorate12, have been described, corresponding to the formal addition of alkyl or acyl hypoiodite across the double bond. However, the formation of free 2-deoxy-2-iodo sugars has not been described hitherto. We now report a formal electrophilic addition of “hypoiodous acid” to 3,4,6-tri0-acetyl-o-glucal’3 (1) and 3,4-di-0-acetyl-6-0-tosyl-D-glucal’4 (2). Depending on the buffer system used and the pH, a mixture of the 2-deoxy-2-iodo esters 3 of 5 together with the corresponding 2-deoxy-2-iodo sugars 4 or 6, or only 4 or 6, were obtained. The compounds obtained could be used for the preparation of 2-deoxy sugars or Brigl’s anhydrides. Thus, treatment of 1 or 2 with iodine in tert-butyl alcohol in the presence of acetate buffer (pH 5, room temperature, 3 h) gave a mixture of the 2-deoxy-2iodo-manno-esters 3 or 5 together with the corresponding Zdeoxy-Ziodo-a-o-mannopyranose derivatives 4 or 6, in the ratio 3 : 1. However, when this reaction was carried out in the presence of a phosphate or carbonate buffer (pH 6-7, room temperature, 3 h), the 2-deoq&iodo-a-D-mannopyranose derivatives 4 or 6 were the only isolable products (50-60%). The structures of 3-6 were confirmed by the NMR data (Table I> and [cu], values. The above procedure for the preparation of the 2-deoxy-2-iodo-cu-D-manno-
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