Hexofuranoses, 1,5-anhydro-, formation

Other studies of selective sulfonylation at a primary hydroxyl group of sugars were made with 5-deoxy-l,2-0-isopropylidene-a-D-xy/o-hexofuranose at —12° to give the 6-p-toluenesulfonate and 6-methanesulfonate. On wanning the reaction mixture to 25°, these derivatives were converted into 3,6-anhydro-5-deoxy-l,2-0-isopropyl-idene-a-D-xyio-hexofuranose. The formation of 2,5-anhydrides on p-toluenesulfonylation of dialkyl dithioacetals of pentoses probably proceeds similarly, through the 5-p-toluenesulfonates. 

In general, on reaction with lithium aluminum hydride, secondary sulfonic esters are desulfonylated, with formation of the corresponding secondary alcohol. An exception is provided in an observation by Reist and coworkers, who treated 6-0-benzoyl-l,2-0-isopropyli-dene-5-O-p-tolylsulfonyl-a-D-glucofuranose, with lithium aluminum hydride in ether and obtained a product thought to be 6-deoxy-l,2-0-isopropylidene-y3-L-idofuranose, derived from an intermediate 5,6-anhydro-L-ido derivative later, Ryan and coworkers showed, from its nuclear magnetic resonance spectrum, that the product was 5-deoxy-l,2-0-isopropylidene-a-D- t/Zo-hexofuranose. The problem has been re-examined by Overend and coworkers the repetition experiment under the conditions of Reist and coworkers afforded 5-deoxy-... 

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