Sequential Ring-Closing Metathesis and Nitrone Cycloaddition on Glucose-Derived Substrates: A Divergent Approach to Analogues of Spiroannulated Carbanucleosides and Conformationally Locked Nucleosides

Sahabuddin, Sk and Roy, Ashim and Drew, Michael G. B and Roy, Biswajit Gopal and Achari, Basudeb and Madal, Sukhendu B (2006) Sequential Ring-Closing Metathesis and Nitrone Cycloaddition on Glucose-Derived Substrates: A Divergent Approach to Analogues of Spiroannulated Carbanucleosides and Conformationally Locked Nucleosides. The Journal of Organic Chemistry, 71 (16). pp. 5980-5992.

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    Abstract

    The carbohydrate-derived substrate 3-C-allyl-1,2:5,6-di-O-isopropylidene-R-D-allofuranose was judiciously manipulated for preparing suitable synthons, which could be converted to a variety of isoxazolidinospirocycles and -tricycles through the application of ring-closing metathesis (RCM) and intramolecular nitrone cycloaddition (INC) reactions. Cleavage of the isoxazolidine rings of some of these derivatives by tranfer hydrogenolysis followed by coupling of the generated amino functionalities with 5-amino- 4,6-dichloropyrimidine furnished the corresponding chloropyrimidine nucleosides, which were elaborated to spiroannulated carbanucleosides and conformationally locked bicyclo[2.2.1]heptane/oxa-bicyclo[3.2.1]- octane nucleosides. However, use of higher temperature for the cyclization of one of the chloropyrimidines led to the dimethylaminopurine analogue as a sole product, formed via nucleophilic displacement of the chloro group by dimethylamine generated from DMF.

    Item Type: Article
    URI: http://www.eprints.iicb.res.in/id/eprint/405
    Subjects: Chemistry
    Divisions: Indian Institute of Chemical Biology
    Depositing User: Ms Sutapa Ganguly
    Date Deposited: 01 Nov 2011 11:18
    Last Modified: 15 Jan 2013 11:45
    Official URL: http://dx.doi.org/10.1021/jo0606554 CCC: $33.50
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