Overturning established chemoselectivities: selective reduction of arenes over malonates and cyanoacetates by photoactivated organic electron donors

Eswararao Doni, Bhaskar Mondal, Steven O'Sullivan, Tell Tuttle, John A Murphy

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The prevalence of metal-based reducing reagents, including metals, metal complexes, and metal salts, has produced an empirical order of reactivity that governs our approach to chemical synthesis. However, this reactivity may be influenced by stabilization of transition states, intermediates, and products through substrate-metal bonding. This article reports that in the absence of such stabilizing interactions, established chemoselectivities can be overthrown. Thus, photoactivation of the recently developed neutral organic superelectron donor 5 selectively reduces alkyl-substituted benzene rings in the presence of activated esters and nitriles, in direct contrast to metal-based reductions, opening a new perspective on reactivity. The altered outcomes arising from the organic electron donors are attributed to selective interactions between the neutral organic donors and the arene rings of the substrates.
Original languageEnglish
Pages (from-to)10934-10937
Number of pages4
JournalJournal of the American Chemical Society
Issue number30
Early online date16 Jul 2013
Publication statusPublished - 31 Jul 2013


  • established chemoselectivities
  • selective reduction
  • arenes
  • photoactivated
  • organic electron donors
  • malonates
  • cyanoacetates

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