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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.
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 language | English |
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Pages (from-to) | 3731−3746 |
Number of pages | 16 |
Journal | Journal of Organic Chemistry |
Volume | 79 |
Issue number | 9 |
DOIs | |
Publication status | Published - 2 May 2014 |
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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Dive into the research topics of 'Discovery and development of organic super-electron-donors'. Together they form a unique fingerprint.Projects
- 1 Finished
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Light-Activated Approaches to Highly Challenging Organic Electron Transfer Reactions
Murphy, J. & Zhou, S.
EPSRC (Engineering and Physical Sciences Research Council)
1/07/13 → 30/06/15
Project: Research