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Radical/Polar Annulation Reactions (RPARs) Enable the Modular Construction of Cyclopropanes
John A Milligan1, James P Phelan1, Viktor C Polites1
1Roy and Diana Vagelos Laboratories, Department of Chemistry , University of Pennsylvania , 231 South 34th Street , Philadelphia , Pennsylvania 19104-6323 , United States.
Abstract:
An annulation process for the construction of 1,1-disubstituted cyclopropanes via a radical/polar crossover process is described. The cyclopropanation proceeds by the addition of a photocatalytically generated radical to a homoallylic tosylate. Reduction of the intermediate radical alkylation adduct (via single electron transfer) furnishes an anion that undergoes an intramolecular substitution. The process displays excellent functional group tolerance, characteristic of proceeding through odd-electron intermediates, and occurs under mild conditions with visible light irradiation.
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