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Mild Isomerization of Conjugated Dienes Using Co-Mediated Hydrogen Atom Transfer

Kyle R. Delgado, Dustin D. Youmans, Steven T. Diver

2020Organic Letters30 citationsDOI

Abstract

A mild and high yielding rearrangement of 1,3-disubstituted-1,3-dienes to 1,1,4-trisubstituted-1,3-dienes using a cobaloxime catalyst and a silane cocatalyst is reported. Chiral centers near the conjugated diene were not racemized. Deuterium labeling studies are consistent with a hydrogen atom transfer mechanism, and radical intermediates were found to be accessible due to the observed ring opening of a cyclopropane ring.

Topics & Concepts

ChemistryIsomerizationCyclopropaneHydrogen atomRing (chemistry)Conjugated systemPhotochemistryCatalysisHydrogenDeuteriumSilaneMedicinal chemistryOrganic chemistryPolymerQuantum mechanicsPhysicsAlkylMetalloenzymes and iron-sulfur proteinsAsymmetric Hydrogenation and CatalysisCO2 Reduction Techniques and Catalysts
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