A plethora of isomerization processes and hydrogen scrambling in the fragmentation of the methanol dimer cation: a PEPICO study

The valence photoionization of light and deuterated methanol dimers was studied by imaging photoelectron photoion coincidence spectroscopy in the 10.00–10.35 eV photon energy range. Methanol clusters were generated in a...

E-Olefins through intramolecular radical relocation

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, incompleteE/Zstereoselection, and/or high cost. Here, we report a fundamentally different, radical-based approach. We showcase a nonprecious, reductant-free, and atom-economical nickel (Ni)(I)-catalyzed intramolecular 1,3-hydrogen atom relocation to yieldE-olefins within 3 hours at room temperature. Remote installations ofE-olefins over extended distances are also demonstrated.