ArticleJournal of the American Chemical Society2026
Enantioselective Contrathermodynamic Olefin Isomerization.
Article in Journal of the American Chemical Society, 2026. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Not yet cited in PubMed.
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5 authors.
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Abstract
A light-driven method for the enantioselective contrathermodynamic positional isomerization of olefins based on excited-state electron transfer is reported. Sequential oxidation and deprotonation of a tetrasubstituted enol ether generates an allylic radical which is captured by a Cr(II) cocatalyst bearing a chiral bioxazoline (BiOX) ligand. Regio- and enantioselective protodemetalation of the nascent Cr(III) allyl complex by methanol yields the terminal olefin product with enantioselectivities of up to 95:5 er. Kinetic and isotopic labeling studies support an enantiodetermining protodemetalation and reveal the presence of two primary KIEs within the same catalytic manifold.
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Registered trials
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