Discovery and development of organic super-electron-donors

Research output: Contribution to journalArticle

79 Citations (Scopus)

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.
LanguageEnglish
Pages3731−3746
Number of pages16
JournalJournal of Organic Chemistry
Volume79
Issue number9
DOIs
Publication statusPublished - 2 May 2014

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Benzene
Anions
Malonates
Aromatization
Electrons
Alkenes
Amides
Ground state
Functional groups
Transition metals
Chlorides
Metals
Derivatives
acyloin
ethylene

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

Cite this

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title = "Discovery and development of organic super-electron-donors",
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.",
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",
author = "Murphy, {J. A.}",
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Discovery and development of organic super-electron-donors. / Murphy, J. A.

In: Journal of Organic Chemistry, Vol. 79, No. 9, 02.05.2014, p. 3731−3746.

Research output: Contribution to journalArticle

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N2 - 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.

AB - 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.

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KW - nucleophilic trifluoromethylation

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KW - aryl iodides

KW - samarium(ii) iodide

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