title: Metal Bridging for Directing and Accelerating Electron Transfer as Exemplified by Harnessing the Reactivity of AIBN.
abstract: A new strategy for tuning the electron transfer between radicals and enolates has been developed. This method elicits the innate reactivity of AIBN with a copper catalyst and enables a cascade reaction with cinnamic acids. Electron paramagnetic resonance studies and control experiments indicate that the redox-active copper species not only activates the radical by coordination, but also serves as a bridge to bring the radical and nucleophile within close proximity to facilitate electron transfer. By exploiting possible combinations of redox-active metals and radical entities with suitable coordinating functional groups, this strategy should contribute to the development of a broad range of radical-based reactions.
authors: State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China).
authors: Yinjun
authors: Y
authors: Xie
authors: Shengmei
authors: S
authors: Guo
authors: Longmin
authors: L
authors: Wu
authors: Chungu
authors: C
authors: Xia
authors: Hanmin
authors: H
authors: Huang
mesh_terms: D003300:Copper / Q000737:chemistry*; D004578:Electron Spin Resonance Spectroscopy; D004579:Electron Transport; D015394:Molecular Structure; D009570:Nitriles / Q000737:chemistry*
chemical_list: D009570:Nitriles; D003300:Copper; C004526:azobis(isobutyronitrile)
keywords: AIBN; cinnamic acids; copper; enolates; single-electron transfer