Abstract
The first enantioselective total syntheses of crotonine G and crotonolide D are disclosed. The synthetic approach employs a SmI2 mediated ketyl radical cyclization to form the highly congested quaternary carbon at the center of these complex molecules. Following the furan introduction, the core structure of the natural product is con-structed via oxidative olefin cleavage to install the unusual C-19 and C-20 oxidation. Finally, palladium catalyzed carbonylation, furan oxidation and acid mediated condensation/epimerization completes the synthesis.
Supplementary materials
Title
experimentals and spectra
Description
experimental and spectra
Actions
Title
Computed structures
Description
Computed structures
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Title
QM energies
Description
QM energies
Actions