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Room temperature photo-promoted iron-catalysed arene C–H alkenylation without Grignard reagents

  • Antonis M. Messinis,
  • Tristan von Münchow,
  • Max Surke,
  • Lutz Ackermann

摘要

Iron is inexpensive, non-toxic and the most abundant transition metal in the Earth’s crust, rendering iron-catalysed C–H activations attractive yet particularly challenging. Despite major advances, iron-catalysed C–H activations have been linked to high reaction temperatures or the use of reactive Grignard reagents. Here we present iron-catalysed ketimine C–H activations at ambient reaction temperature with the help of blue light in the absence of additives, utilizing easily accessible cis-[Fe(H)2(dppe)2] (where dppe is 1,2-bis(diphenylphosphino)ethane) as a single component precatalyst. Mild reaction conditions, high atom economy and the lack of Grignard reagents are distinguishing features of the iron-catalysed C–H alkenylation manifold. Detailed mechanistic investigations by deuterium labelling, isolation of organometallic intermediates and in operando light-emitting diode nuclear magnetic resonance spectroscopy revealed the role of the light and an oxidative addition to an iron(0) complex as the modus operandi for the C–H activation.