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Total Synthesis Of Cephalosporolide E Via A Tandem Radical/polar Crossover Reaction. The Use Of The Radical Cations Under Nonoxidative Conditions In Total Synthesis.

Omar Cortezano-Arellano, L. Quintero, Fernando Sartillo-Piscil
Published 2015 · Chemistry, Medicine

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The present work reports the first example of the use of the chemistry of radical cations under nonoxidative conditions in total synthesis. Using a late-stage tandem radical/polar crossover reaction, a highly stereoselective total synthesis of cephalosporolide E (which is typically obtained admixed with cephalosporolide F) was accomplished. The reaction of a phthalimido derivative with triphenyltin radical in refluxing toluene engenders a contact ion-pair (radical cation) that leads, in the first instance, to the cephalosporolide F, which is transformed into the cephalosporolide E via a stereocontrolled spiroketal isomerization promoted by the diphenylphosphate acid that is formed during the tandem transformation.
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