Carbohydrate Research 1991-09-02

Thio and epidithio derivatives of methyl beta-lactoside.

M A Ali, L Hough, A C Richardson

Index: Carbohydr. Res. 216 , 271-87, (1991)

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Abstract

Treatment of methyl beta-lactoside with triphenylphosphine-carbon tetrabromide in pyridine gave the 3',6'-anhydro-6-bromo-6-deoxy derivative, from which 6-thio derivatives were prepared, and methyl 3',4'-O-isopropylidene-beta-lactoside gave the 6,6'-dibromo-6,6'-dideoxy derivative. A dibromide was prepared also from methyl 4',6'-O-benzylidene-beta-lactoside by bromination with Ph3P-CBr4, acetylation, and then treatment with N-bromosuccinimide. Various 6,6'-dithio derivatives were prepared from the 6,6'-dibromide by nucleophilic substitution reactions. Reaction of the 6,6'-dibromide with thiourea led to the 6,6'-epidithio derivative and, with potassium tricarbonate, the bridged 6,6'-trithiocarbonate was formed. The 6,6'-dibromo derivative underwent selective nucleophilic substitution to give a variety of 6'-bromo-6-thio derivatives. Likewise, with azide, the 6-azide was formed first, followed by the 6,6'-diazide and the product of elimination, the 6-azido-5%-ene. Raney nickel-mediated desulphuration of the various 6,6'-dithio derivatives afforded methyl 6,6'-dideoxy-beta-lactoside and desulphuration of the 6'-bromo-6-thio derivatives could be accomplished without reductive dehalogenation to give methyl 6'-bromo-6,6'-dideoxylactoside.