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Reactions with and in Anydrous Hydrogen Fluoride, 13. A Convenient One‐Pot Synthesis of Glucofurano[2,1‐ d ]oxazolines with an Additional 3,5,6‐Orthoester Function
Author(s) -
Miethchen Ralf,
Klein Holger,
Pedersen Christian
Publication year - 1994
Publication title -
liebigs annalen der chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 0170-2041
DOI - 10.1002/jlac.199419940922
Subject(s) - chemistry , triethylamine , acetic anhydride , diethylamine , orthoester , hydrogen fluoride , organic chemistry , anhydrous , hydrogen chloride , chloride , acetyl chloride , moiety , formic acid , medicinal chemistry , catalysis
The reactions of dioxolanylium and oxazolinium ions, formed in anhydrous HF from N ‐acylated 2‐amino‐2‐deoxy‐ D ‐glucoses and one equivalent of carboxylic acid anhydride or chloride, were investigated by treatment of their HF solutions with triethylamine/alkane or triethylamine/ether systems. Thus, the 2‐acylamido‐2‐deoxy‐ D ‐glucoses 1 and 2 react with acetic anhydride, dodecanoic anhydride or pivaloyl chloride in anhydrous HF at −30°C to give 5,6‐dioxolanylium ions. On treatment with formic acid at room temperature they undergo further reaction to yield the thermodynamically favored 3,6‐anhydro derivatives. The glucofurano‐oxazolines 3–5 , containing an orthoester substructure, as well as the 3,6‐anhydro‐ D ‐glucofuranose derivatives 6 and 7 can be isolated after treatment of the HF solutions with triethylamine. The oxazoline derivative 4 was used as glycosyl donor for methanol giving the methyl glycoside 8 without cleavage of the orthoester moiety.