Linear fused pyran-dioxane-cyclohexane tricycles: Synthesis of the five linkage isomers and ensuing reactions

European Journal of Organic Chemistry

Volumn , Issue 23, 2004, Pages 4911-4920

  Lichtenthaler, Frieder W ^a   Cuny, Eckehard ^a  

^a DARMSTADT UNIVERSITY OF TECHNOLOGY   (Germany)

Author keywords

Carbohydrates; Glycosylation; Trioxa perhydroanthracenes; Ulosyl bromides

Indexed keywords

2 KETOHEXOSYL BROMIDE; ACETAL; ANTHRACENE DERIVATIVE; BETA 2 KETOGLYCOSIDE; BORON TRIFLUORIDE; BROMINE DERIVATIVE; CARBOHYDRATE DERIVATIVE; CARDENOLIDE; CARDIAC GLYCOSIDE; CYCLOHEXAN 1,2 DIOL; CYCLOHEXANE DERIVATIVE; DIOXANE; FUSED HETEROCYCLIC RINGS; GLUCOSE DERIVATIVE; GLYCOSIDE; HYDROXYL GROUP; PYRAN; SILANE DERIVATIVE; SPECTINOMYCIN; TRIETHYLSILANE; TRIOXAPERHYDROANTHRACENE DERIVATIVE; ULOSYL BROMIDE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; GEOMETRY; GLYCOSYLATION; HEMIKETALIZATION; ISOMER; METHODOLOGY; PROTON NUCLEAR MAGNETIC RESONANCE; STEREOCHEMISTRY; SYNTHESIS;

EID: 10844294986     PISSN: 1434193X     EISSN: None     Source Type: Journal    
DOI: 10.1002/ejoc.200400457     Document Type: Article

References (28)

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23. N2-typehydride attack on the tertiary carbon (C-4a) of the OH-activated intermediate (e.g. II), as the rigidity of the tricyclic ring system precludes inversion at C-4a. The reaction must thus proceed through a carboxonium ion (e.g. III), which adds hydride, e.g. II → III → 15. Accordingly, the OH groups in 10 and 12 are replaced by hydrogen with retention of configuration, thereby verifying the linkage geometry conclusions drawn from NOE effects of the cis-transoid-cis (10/14) and the cis-cisoid-cis pairs 12/15 (Scheme 3).
24. CCDC-224773 contains the supplementary crystallographic data for 16. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/ retrieving.html [or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; Fax: +44-1223-336-033; E-mail: deposit@ccdc.cam.ac. uk].
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28. An attractive possibility for the biosynthesis of cardenolides of type 1, 3 and 4, as well as of spectinomycin (2), implies monoglycosylation of the steroidal diol aglycon or of actinamine, oxidation of the respective 6-deoxy-glycosides to the glycosiduloses which - in nonenzyme-mediated fashion - undergo intramolecular hemiketalization.