Simple Synthesis of 1,2-Dideoxy-2-Vinyl Carbohydrates by Tin-Free Radical Reactions of Xanthates.

Vinyl-substituted carbohydrates have been synthesized from glycals derived from hexoses and pentoses. Key step is the radical reaction of xanthates in the presence of triethylborane, a non-toxic reagent. The mechanism has been investigated by isolation of various side products, which speak for a reversibility of the cyclopropylmethyl radical ring-opening. Compared to reactions with tributyltin hydride, higher regioselectivities in favor of the 2-vinyl-substituted sugars have been obtained. Yields are slightly lower with triethylborane, but all products have been isolated in analytically pure form. The new reaction is applicable to benzyl- and silyl-protected carbohydrates, which makes free sugars accessible as well. Overall, more than 15 1,2-dideoxy-2-vinyl carbohydrates have been synthesized from simple precursors in only few steps.