Abstract
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.
| Language | English |
|---|---|
| Pages | 3731−3746 |
| Number of pages | 16 |
| Journal | Journal of Organic Chemistry |
| Volume | 79 |
| Issue number | 9 |
| DOIs | |
| Publication status | Published - 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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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 journal › Article
TY - JOUR
T1 - Discovery and development of organic super-electron-donors
AU - Murphy, J. A.
PY - 2014/5/2
Y1 - 2014/5/2
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.
KW - polar crossover reactions
KW - free reductive cleavage
KW - c-h activation
KW - tetrakis(dimethylamino)ethylene tdaec-h activation
KW - nucleophilic trifluoromethylation
KW - diazonium salts
KW - aryl iodides
KW - samarium(ii) iodide
KW - aldehydes
UR - http://pubs.acs.org/journal/joceah
U2 - 10.1021/jo500071u
DO - 10.1021/jo500071u
M3 - Article
VL - 79
SP - 3731−3746
JO - Journal of Organic Chemistry
T2 - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 9
ER -