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Updated: May 3, 2026

Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers
Published on: December 16, 2022
Enantioselective Contrathermodynamic Olefin Isomerization
Bianca L Imbriaco1, Sumin Lee1, Eve Yuanwei Xu1
1Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
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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