10.1021/ol006714w.s001 Philomena M. Enright Philomena M. Enright Kathy M. O'Boyle Kathy M. O'Boyle Paul V. Murphy Paul V. Murphy Synthesis of d-Hexos-5-uloses by Novel in Situ Hydrolysis of Epoxides Derived from 6-Deoxyhex-5-enopyranosides American Chemical Society 2000 bicyclic solution dicarbonyl precursor Situ Hydrolysis anhydropyrano ketoglucose hexo biosynthesi Deoxyhex methodology inositol derivative ketohexose pyranose ring Synthesi deoxynojirimycin 4 C 1 conformation Epoxides Derived tri yield xylo 2000-11-03 00:00:00 Journal contribution https://acs.figshare.com/articles/journal_contribution/Synthesis_of_d-Hexos-5-uloses_by_Novel_in_Situ_Hydrolysis_of_Epoxides_Derived_from_6-Deoxyhex-5-enopyranosides/3737559 Epoxides derived from 2,3,4-tri-<i>O</i>-protected-6-deoxyhex-5-enopyranosides are hydrolyzed in situ to ultimately give novel protected-d-hexos-5-ulose derivatives (sugar 1,5-dicarbonyls, 5-ketohexoses) in moderate to high yields. The products adopt a bicyclic structure (1,6-anhydropyranos-5-ulose) in solution with the pyranose ring in <sup>4</sup><i>C</i><sub>1</sub> conformation. The methodology has been used to prepare d-<i>xylo</i>-hexos-5-ulose (5-ketoglucose), a synthetic precursor to 1-deoxynojirimycin and a possible intermediate in the biosynthesis of inositols.