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From D ‐Glucose to Biologically Potent L ‐Hexose Derivatives: Synthesis of α‐ L ‐Iduronidase Fluorogenic Detector and the Disaccharide Moieties of Bleomycin A 2 and Heparan Sulfate
Author(s) -
Lee JinqChyi,
Chang ShuWen,
Liao ChihCheng,
Chi FaChen,
Chen ChienSheng,
Wen YuhSheng,
Wang ChengChung,
Kulkarni Suvarn S.,
Puranik Ramachandra,
Liu YiHung,
Hung ShangCheng
Publication year - 2004
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200305096
Subject(s) - disaccharide , chemistry , chitobiose , hexose , biochemistry , enzyme , chitin , chitosan
A novel and convenient route for the synthesis of biologically potent and rare L ‐hexose derivatives from D ‐glucose is described. Conversion of diacetone‐α‐ D ‐glucose ( 14 ) into 1,2:3,5‐di‐ O ‐isopropylidene‐β‐ L ‐idofuranose ( 19 ) was efficiently carried out in two steps. Orthogonal isopropylidene rearrangement of compound 19 led to 1,2:5,6‐di‐ O ‐isopropylidene‐β‐ L ‐idofuranose ( 27 ), which underwent regioselective epimerization at the C3 position to give the L ‐talo‐ and 3‐functionalized L ‐idofuranosyl derivatives. Hydrolysis of compound 19 under acidic conditions furnished 1,6‐anhydro‐β‐ L ‐idopyranose ( 35 ) in excellent yield, which was successfully transformed into the corresponding L ‐ allo , L ‐ altro , L ‐ gulo , and L ‐ ido derivatives via regioselective benzylation, benzoylation, triflation and nucleophilic substitution as the key steps. Applications of these 1,6‐anhydro‐β‐ L ‐hexopyranoses as valuable building blocks to the syntheses of 4‐methylcoumarin‐7‐yl‐α‐ L ‐iduronic acid and the disaccharide moieties of bleomycin A 2 as well as heparan sulfate are highlighted.