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Discovery and Development of Organic Super-Electron-Donors

[Image: see text] 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 c...

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Autor principal: Murphy, John A.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2014
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4010563/
https://www.ncbi.nlm.nih.gov/pubmed/24605904
http://dx.doi.org/10.1021/jo500071u
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author Murphy, John A.
author_facet Murphy, John A.
author_sort Murphy, John A.
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description [Image: see text] 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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spelling pubmed-40105632014-05-06 Discovery and Development of Organic Super-Electron-Donors Murphy, John A. J Org Chem [Image: see text] 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. American Chemical Society 2014-03-07 2014-05-02 /pmc/articles/PMC4010563/ /pubmed/24605904 http://dx.doi.org/10.1021/jo500071u Text en Copyright © 2014 American Chemical Society Terms of Use CC-BY (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html)
spellingShingle Murphy, John A.
Discovery and Development of Organic Super-Electron-Donors
title Discovery and Development of Organic Super-Electron-Donors
title_full Discovery and Development of Organic Super-Electron-Donors
title_fullStr Discovery and Development of Organic Super-Electron-Donors
title_full_unstemmed Discovery and Development of Organic Super-Electron-Donors
title_short Discovery and Development of Organic Super-Electron-Donors
title_sort discovery and development of organic super-electron-donors
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4010563/
https://www.ncbi.nlm.nih.gov/pubmed/24605904
http://dx.doi.org/10.1021/jo500071u
work_keys_str_mv AT murphyjohna discoveryanddevelopmentoforganicsuperelectrondonors