RESUMEN
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.
RESUMEN
The photooxygenation of 1,4-cyclohexadienes has been studied with a special focus on regio- and stereoselectivities. In all examples, only the methyl-substituted double bond undergoes an ene reaction with singlet oxygen, to afford hydroperoxides in moderate to good yields. We explain the high regioselectivities by a "large-group effect" of the adjacent quaternary stereocenter. Nitriles decrease the reactivity of singlet oxygen, presumably by quenching, but can stabilize proposed per-epoxide intermediates by polar interactions resulting in different stereoselectivities. Spiro lactams and lactones show an interesting effect on regio- and stereoselectivities of the ene reactions. Thus, singlet oxygen attacks the double bond preferentially anti to the carbonyl group, affording only one regioisomeric hydroperoxide. If the reaction occurs from the opposite face, the other regioisomer is exclusively formed by severe electrostatic repulsion in a perepoxide intermediate. We explain this unusual behavior by the fixed geometry of spiro compounds and call it a "spiro effect" in singlet oxygen ene reactions.
RESUMEN
Carbohydrate radical stabilities in the 1- and 2-position have been determined by a radical clock approach, starting from cyclopropanated sugars with xanthates as precursors. Various hexoses and pentoses afforded 1-deoxy sugars as main products, indicating that anomeric radicals are more stable than radicals in the 2-position. An additional influence of the configurations on radical stabilities has been observed. Our results should be interesting for the understanding of 1,2-radical rearrangements in carbohydrate chemistry and offer an easy access to deoxy-vinyl sugars.