THE REACTION OF UNSATURATED CARBOHYDRATES WITH CARBON MONOXIDE AND HYDROGEN: II. STRUCTURE AND STEREOCHEMISTRY OF THE ANHYDRODEOXYHEXITOLS FROM 3,4-DI-O-ACETYL-D-XYLAL

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Abstract
3,4-Di-O-acetyl-D-xylal reacted with carbon monoxide and hydrogen in the presence of dicobalt octacarbonyl to yield 1,5-anhydro-4-deoxy-D-arabino-hexitol (I) and 1,5-anhydro-4-deoxy-L-xylo-hexitol (II). The stereochemistry at C-5 of the hexitols was elucidated by correlation with the triol ether (VI) obtained by sodium borohydride reduction of the periodate oxidation product of 1,4-anhydro-5-deoxy-D-arabino-hexitol (VII). Reaction of 3,4-di-O-acetyl-D-xylal with carbon monoxide and deuterium afforded 1,5-anhydro-4-deoxy-D-arabino-hexitol-4,6,6-H32 (VIII) and 1,5-anhydro-4-deoxy-L-xylo-hexitol-4,6,6-H32 (IX). Examination of the nuclear magnetic resonance (n.m.r.) spectra of the normal and deuterated anhydrodeoxyhexitols confirmed the structural assignments and showed that cis-addition to the double bond takes place to give (IX).