Total Synthesis of GracilioetherF: Development and Application of Lewis Acid Promoted Ketene-Alkene [2+2]Cycloadditions and Late-Stage C--H Oxidation

The first synthesis of gracilioetherF, a polyketide natural product with an unusual tricyclic core and five contiguous stereocenters, is described. Key steps of the synthesis include a Lewis acid promoted ketene-alkene [2+2]cycloaddition and a late-stage carboxylic acid directed C(sp super(3))--H ox...

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Bibliographic Details
Published inAngewandte Chemie International Edition Vol. 53; no. 52; pp. 14522 - 14526
Main Authors Rasik, Christopher M, Brown, MKevin
Format Journal Article
LanguageEnglish
Published 01.12.2014
Subjects
Carboxylic acids
Ketenes
Lewis acid
Natural products
Olefins
Oxidation
Synthesis
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Summary:The first synthesis of gracilioetherF, a polyketide natural product with an unusual tricyclic core and five contiguous stereocenters, is described. Key steps of the synthesis include a Lewis acid promoted ketene-alkene [2+2]cycloaddition and a late-stage carboxylic acid directed C(sp super(3))--H oxidation. The synthesis requires only eight steps from norbornadiene. Controlled oxidation: GracilioetherF can be synthesized from norbornadiene in only eight steps while avoiding the use of protecting groups. Key steps of the synthesis include a Lewis acid promoted [2+2]cycloaddition of a ketene with an olefin and a late-stage carboxylic acid directed C(sp super(3))--H oxidation.
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ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201408055