Olefin shuffle for just a nickel: Controlling the geometry of carbon-carbon double bonds is a central component of chemical manufacturing. One useful trick is to shift hydrogen atoms around to interconvert C=C isomers selectively. However, this approach typically requires precious metals. Kapat et al. now report that more-abundant nickel can catalyze rapid conversion of terminal olefins into internal olefins with high selectivity for trans geometry. The odd-electron nickel complex relies on a radical mechanism to shuttle hydrogen to the terminal carbon from the saturated carbon adjacent to the double bond. Science , this issue p. 391

We report a remote functionalization strategy, which allows the Z-selective synthesis of silyl enol ethers of (hetero)aromatic and aliphatic ketones via Ni-catalyzed chain walking from a distant olefin site. The positional selectivity is controlled by the directionality of the chain walk and is independent of thermodynamic preferences of the resulting silyl enol ether. Our mechanistic data indicate that a Ni^(I) dimer is formed under these conditions, which serves as a catalyst resting state and, upon reaction with an alkyl bromide, is converted to [Ni^(II)-H] as an active chain-walking/functionalization catalyst, ultimately generating a stabilized η³-bound Ni^(II) enolate as the key selectivity-controlling intermediate.