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Organofluorverbindungen und Fluorierungsagenzien, 9. Von Glycosylfluoriden zu chiralen Kronenethern
Author(s) -
Miethchen Ralf,
Gabriel Torsten
Publication year - 1993
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19931261020
Subject(s) - chemistry , glycosyl , fluoride , aldose , medicinal chemistry , stereochemistry , organic chemistry , glycoside , inorganic chemistry
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 as the trans ‐decalin analog 1,2‐ O ‐ethanediyl‐3,4,6‐tri‐ O ‐methyl‐β‐ D ‐glucopyranose ( 13 ) are selectively transformed with deacetalisation into the corresponding acylated glycosyl fluorides 2, 4, 6a—g, 8 , and 14 by HF/nitro‐methane/carboxylic acid anhydride. The reaction is realized without change of the ring size if the three‐component agent system is mixed some time before the carbohydrate is added. 3,5,6‐Tri‐ O ‐methyl‐2‐ O ‐pivaloyl‐D‐glucofuranosyl fluoride ( 8 ) and 2‐ O ‐(2‐acetoxyethyl)‐3,4,6‐tri‐ O ‐methyl‐α‐ D ‐glucosyl fluoride ( 14 ) are used as starting materials to synthesize three isomeric, chiral crown ethers, the bis‐β‐D‐glucofuranosido‐12‐crown‐4 derivative 12 and both stereoisomeric bis‐ D ‐glucopyranosido‐12‐crown‐4 derivatives 20 and 21 .