Organofluorverbindungen und Fluorierungsagenzien, 9. Von Glycosylfluoriden zu chiralen Kronenethern

摘要: Organofluorine Compounds and Fluorinating Agents, 9[1a]. — From Glycosyl Fluorides to Chiral Crown Ethers Methyl D-galactofuranoside (1), methyl D-glucofuranoside (3), 3-O-substituted 1,2:5,6-di-O-isopropylidene-α-D-glucofuranoses (5a—g), 1,2-O-isopropylidene-3,5,6-tri-O-methyl-α-D-glucofuranose (7) as well the trans-decalin analog 1,2-O-ethanediyl-3,4,6-tri-O-methyl-β-D-glucopyranose (13) are selectively transformed with deacetalisation into corresponding acylated glycosyl fluorides 2, 4, 6a—g, 8, 14 by HF/nitro-methane/carboxylic acid anhydride. The reaction is realized without change of ring size if three-component agent system mixed some time before carbohydrate added. 3,5,6-Tri-O-methyl-2-O-pivaloyl-D-glucofuranosyl fluoride (8) 2-O-(2-acetoxyethyl)-3,4,6-tri-O-methyl-α-D-glucosyl (14) used starting materials synthesize three isomeric, chiral crown ethers, bis-β-D-glucofuranosido-12-crown-4 derivative 12 both stereoisomeric bis-D-glucopyranosido-12-crown-4 derivatives 20 21.