Discovery and development of organic super-electron-donors

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Abstract

Based on simple ideas of electron-rich alkenes, exemplified by tetrakis(dimethylamino)ethene, TDAE, and on additional driving force associated with aromatization, families of very powerful neutral organic super-electron-donors (SEDs) have been developed. In the ground state, they carry out metal-free reductions of a range of functional groups. Iodoarenes are reduced either to aryl radicals or, with stronger donors, to aryl anions. Reduction to aryl radicals allows the initiation of very efficient transition-metal-free coupling of haloarenes to arenes. The donors also reduce alkyl halides, arenesulfonamides, triflates,
and triflamdes, Weinreb amides, and acyloin derivatives. Under photoactivation at 365 nm, they are even more powerful and reductively cleave aryl chlorides. They reduce unactivated benzenes to the corresponding radical anions and display original selectivities in preferentially reducing benzenes over malonates or cyanoacetates. Additionally, they reductively cleave ArC−X, ArX−C (X = N or O) and ArC−C bonds, provided that the two resulting fragments are somewhat stabilized.
Original languageEnglish
Pages (from-to)3731−3746
Number of pages16
JournalJournal of Organic Chemistry
Volume79
Issue number9
DOIs
Publication statusPublished - 2 May 2014

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Keywords

  • polar crossover reactions
  • free reductive cleavage
  • c-h activation
  • tetrakis(dimethylamino)ethylene tdaec-h activation
  • nucleophilic trifluoromethylation
  • diazonium salts
  • aryl iodides
  • samarium(ii) iodide
  • aldehydes

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