Chemical Modification of a Highly Functionalized Taxane. The Consequences of an Absent Bridgehead Double Bond on Oxetane D-Ring Construction

An oxetane D-ring has been fused to the framework of the highly functionalized taxane 2. The synthetic route is based on a trimethylsilyl triflate-promoted epoxide-opening step, followed by stereocontrolled, regioreversed oxirane formation and reductive transposition of this intermediate with bis(cy...

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Bibliographic Details
Published in:Journal of organic chemistry 2003-03, Vol.68 (6), p.2282-2289
Main Authors: Paquette, Leo A, Lo, Ho Yin
Format: Article
Language:English
Subjects:
Alicyclic compounds, terpenoids, prostaglandins, steroids
Bridged-Ring Compounds - chemical synthesis
Bridged-Ring Compounds - chemistry
Catalysis
Chemistry
Combinatorial Chemistry Techniques
Cyclization
Exact sciences and technology
Indicators and Reagents
Molecular Structure
Nuclear Magnetic Resonance, Biomolecular
Organic chemistry
Oxidation-Reduction
Paclitaxel - chemistry
Preparations and properties
Structure-Activity Relationship
Taxoids
Terpenoids
Thermodynamics
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Summary:An oxetane D-ring has been fused to the framework of the highly functionalized taxane 2. The synthetic route is based on a trimethylsilyl triflate-promoted epoxide-opening step, followed by stereocontrolled, regioreversed oxirane formation and reductive transposition of this intermediate with bis(cyclopentadienyl)titanium(III) chloride. This last key step provides for the convenient implementation of additional hydroxyl groups ultimately conducive to intramolecular SN2 reaction. Tangential features of the route outlined herein include specific rearrangement reactions and a retro-aldol cleavage of ring A.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo0206566