Synthesis of Natural and Unnatural Enantiomers of Goniofufurone and Its 7-Epimers from D-Glucose. Application of Palladium(II) - Catalyzed Oxycarbonylation of Unsaturated Polyols

Tibor Gracza; Volker Jäger

doi:10.1055/s-1994-25694

Synthesis 1994; 1994(12): 1359-1368
DOI: 10.1055/s-1994-25694

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Synthesis of Natural and Unnatural Enantiomers of Goniofufurone and Its 7-Epimers from D-Glucose. Application of Palladium(II) - Catalyzed Oxycarbonylation of Unsaturated Polyols

Tibor Gracza^* , Volker Jäger

^*Department of Organic Chemistry, Slovak Technical University, Radlinského 9, 812 37 Bratislava, Slovakia

Abstract

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Syntheses of 3,6-anhydro-2-deoxy-7-phenylglyconolactones (+)-1 and (+)-2 with D- and L-glycero-D-ido configuration, respectively, as well as of their enantiomers (-)-1 and (-)-2, from D-glucose are presented. The key steps are, (i) phenylmagnesium bromide additions to C1 or C5 of glucose-derived aldehydes 7 and 10, respectively, and (ii), palladium (II)-catalyzed oxycarbonylation of intermediate 1-phenyl-D- and -L-5-hexenitols 8/9 or 14/15. The syntheses proceed in 7 steps with 6% and 18% over-all yield for (+)-1/ (+)-2, and in 6 steps/ 11% and 16% for (-)-1/ (-)-2 ( from monoacetone glucose). The absolute configurations of goniofufurone (+)-1 and its 7-epimer (+)-2 thus established are in accord with those of all suggested biogenetic precursors and allowed, e.g., to propose the absolute configuration of (+)-goniopypyrone, a related cytotoxic, bicyclic styryllactone, and structures of potential biosynthetic intermediates not identified so far.

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