<i>E</i>-Olefins through intramolecular radical relocation.
basic_science · Level V
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- Record sourced from PubMed, PMID 30679370.
- Also identified by DOI 10.1126/science.aav1610.
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Abstract
Full control over the selectivity of carbon-carbon double-bond migrations would enable access to stereochemically defined olefins that are central to the pharmaceutical, food, fragrance, materials, and petrochemical arenas. The vast majority of double-bond migrations investigated over the past 60 years capitalize on precious-metal hydrides that are frequently associated with reversible equilibria, hydrogen scrambling, incomplete <i>E/Z</i> stereoselection, and/or high cost. Here, we report a fundamentally different, radical-based approach. We showcase a nonprecious, reductant-free, and atom-economical nickel (Ni)<sup>(I)</sup>-catalyzed intramolecular 1,3-hydrogen atom relocation to yield <i>E</i>-olefins within 3 hours at room temperature. Remote installations of <i>E</i>-olefins over extended distances are also demonstrated.