Synthesis of Undeculofuranoside Derivatives of the Herbicidins and of Analogues

Article abstract of DOI:10.1021/jo00123a021

The condensation of 3-O-(tert-butyldimethylsilyl)-5-deoxy-1,2-O-isopropylidene-α-D-xylo-hexodialdo-1,4-furanose (obtained in six steps (35percent) from D-glucurono-6,3-lactone) with the lithium enolate of (+/-)-6-endo-chloro-5-endo-(methoxymethoxy)-7-oxabicyclo<2.2.1>heptan-2-one (derived in six steps (25percent) from the Diels-Alder adduct of furan to 1-cyanovinyl acetate) was highly exo face selective giving two major aldols that were separated readily.One of them was converted to 6,10-anhydro-5-deoxy-1,2-O-isopropylidene-9-O-(methoxymethyl)-α-D-arabino-L-ido-7-undeculofuranose-(1,4)-pyranose-(7,3), a semiprotected form of the long-chain carbohydrate moiety of the herbicidins.The synthesis implies the acid-promoted isomerization of 10,11-anhydro-5,7-dideoxy-1,2-O-isopropylidene-9-O-(methoxymethyl)-7-C-<(2-nitrophenyl)selenomethyl>-β-L-ido-L-ido-undecofuranose.