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.

The palladium(II)-catalyzed oxycarbonylation, known with alkenols and alkenediols, is studied with optically active 4-pentenitols (-triols) 1, 7 and 5-hexenitols (-tetrols) 12, 15, 18. Efficient routes for the substrates are provided, mostly from carbohydrate precursors. In all cases, bicyclic 3,6-anhydro-2-deoxy-1, 4-glyconolactones, versatile intermediates of C-glycosidic structure, are isolated with high selectivity and in good yield (53-77%). Several minor products (4-14% of regio-/diastereoisomers) from two competing pathways are observed and identified. The oxycarbonylation of alkenitols thus completes a novel sequence that transforms aldoses into homologous anhydro-glyconolactones, by C₁-elongation at the terminal site. In the key step, the 3,4-threo arrangement is produced, from each of the four diastereomeric alkenitols studied (of the 6 cases available in the C₅ and C₆ series). The stereochemical protocol is summarized, e.g., by the transition D-gluco (aldose) → D-xylo (hexenitol, 15) → L-ido (anhydro-deoxyheptenolactone 26), as demonstrated.

The 3,6-anhydro-2-deoxy-7-phenylglyconolactones (-)-1 and (-)-7 with L-glycero-L-ido and D-glycero-L-ido configuration, respectively, are prepared from monoacetone D-glucose in 6 steps with 11 and 16% yield. Key steps are the phenylmagnesium bromide addition to. unprotected D-xylo-5-hexenose (4), followed by palladium(II)-catalyzed oxycarbonylation of the resulting 1-phenyl-5-hexenitols 5/6. The synthesis of (-)-1 establishes the absolute configuration of the natural antitumor-active goniofufurone (+)-1 as D-glycero-D-ido.

1-(Benzyloxycarbonylamino)-hex-5-en-3-ol (5) undergoes a novel Pd(II)/CuCl₂-catalysed bicyclisation to furnish the corresponding 6-oxa-2-azabicyclo[3.2.1]octane (6) in good yield.