2014
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Oxidative Sequence of a Ruthenocene-Based Anticancer Drug Candidate in a Basic Environment Article de journal Hui Zhi Shirley Lee; Olivier Buriez; Eric Labbe; Siden Top; Pascal Pigeon; Gerard Jaouen; Christian Amatore; Weng Kee Leong Organometallics, 33 (18), p. 4940-4946, 2014. @article{RID:0721150706473-44b,
title = {Oxidative Sequence of a Ruthenocene-Based Anticancer Drug Candidate in a Basic Environment},
author = {Hui Zhi Shirley Lee and Olivier Buriez and Eric Labbe and Siden Top and Pascal Pigeon and Gerard Jaouen and Christian Amatore and Weng Kee Leong},
year = {2014},
date = {2014-01-01},
journal = {Organometallics},
volume = {33},
number = {18},
pages = {4940-4946},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
|
Oxidative sequence of a ruthenocene-based anticancer drug candidate in a basic environment Article de journal Hui Zhi Shirley Lee; Olivier Buriez; Eric Labbé; Siden Top; Pascal Pigeon; Gérard Jaouen; Christian Amatore; Weng Kee Leong Organometallics, 33 (18), p. 4940–4946, 2014. @article{lee2014oxidative,
title = {Oxidative sequence of a ruthenocene-based anticancer drug candidate in a basic environment},
author = {Hui Zhi Shirley Lee and Olivier Buriez and Eric Labb\'{e} and Siden Top and Pascal Pigeon and G\'{e}rard Jaouen and Christian Amatore and Weng Kee Leong},
year = {2014},
date = {2014-01-01},
journal = {Organometallics},
volume = {33},
number = {18},
pages = {4940--4946},
publisher = {American Chemical Society},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
|
Uncovering the Missing Link between Molecular Electrochemistry and Electrocatalysis: Mechanism of the Reduction of Benzyl Chloride at Silver Cathodes Article de journal Oleksiy V Klymenko; Olivier Buriez; Eric Labbé; Dong-Ping Zhan; Sandra Rondinini; Zhong-Qun Tian; Irina Svir; Christian Amatore ChemElectroChem, 1 (1), p. 227-240, 2014. @article{RID:0721150706474-41b,
title = {Uncovering the Missing Link between Molecular Electrochemistry and Electrocatalysis: Mechanism of the Reduction of Benzyl Chloride at Silver Cathodes},
author = {Oleksiy V Klymenko and Olivier Buriez and Eric Labb\'{e} and Dong-Ping Zhan and Sandra Rondinini and Zhong-Qun Tian and Irina Svir and Christian Amatore},
year = {2014},
date = {2014-01-01},
journal = {ChemElectroChem},
volume = {1},
number = {1},
pages = {227-240},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
|
Uncovering the missing link between molecular electrochemistry and electrocatalysis: Mechanism of the reduction of benzyl chloride at silver cathodes Article de journal Oleksiy V Klymenko; Olivier Buriez; Eric Labbé; Dong-Ping Zhan; Sandra Rondinini; Zhong-Qun Tian; Irina Svir; Christian Amatore ChemElectroChem, 1 (1), p. 227–240, 2014. @article{klymenko2014uncovering,
title = {Uncovering the missing link between molecular electrochemistry and electrocatalysis: Mechanism of the reduction of benzyl chloride at silver cathodes},
author = {Oleksiy V Klymenko and Olivier Buriez and Eric Labb\'{e} and Dong-Ping Zhan and Sandra Rondinini and Zhong-Qun Tian and Irina Svir and Christian Amatore},
year = {2014},
date = {2014-01-01},
journal = {ChemElectroChem},
volume = {1},
number = {1},
pages = {227--240},
publisher = {WILEY-VCH Verlag Weinheim},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
|
2013
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Electrochemistry and Supramolecular Interactions of “Ferrocifen” Anticancer Drugs with Cyclodextrins and Lipid Bilayers: An Electrochemical Overview Book Chapter Olivier Buriez; Eric Labbé; Christian Amatore Advances in Organometallic Chemistry and Catalysis, p. 631-651, 2013. @inbook{RID:0721150706474-43,
title = {Electrochemistry and Supramolecular Interactions of “Ferrocifen” Anticancer Drugs with Cyclodextrins and Lipid Bilayers: An Electrochemical Overview},
author = {Olivier Buriez and Eric Labb\'{e} and Christian Amatore},
year = {2013},
date = {2013-01-01},
booktitle = {Advances in Organometallic Chemistry and Catalysis},
pages = {631-651},
keywords = {},
pubstate = {published},
tppubtype = {inbook}
}
|
Electrochemistry and Supramolecular Interactions of “Ferrocifen” Anticancer Drugs with Cyclodextrins and Lipid Bilayers: An Electrochemical Overview Inproceedings Olivier Buriez; Eric Labbé; Christian Amatore Advances in Organometallic Chemistry and Catalysis: The Silver/Gold Jubilee International Conference on Organometallic Chemistry Celebratory Book, p. 631–651, John Wiley & Sons, Inc. Hoboken, NJ, USA 2013. @inproceedings{buriez2013electrochemistry,
title = {Electrochemistry and Supramolecular Interactions of “Ferrocifen” Anticancer Drugs with Cyclodextrins and Lipid Bilayers: An Electrochemical Overview},
author = {Olivier Buriez and Eric Labb\'{e} and Christian Amatore},
year = {2013},
date = {2013-01-01},
booktitle = {Advances in Organometallic Chemistry and Catalysis: The Silver/Gold Jubilee International Conference on Organometallic Chemistry Celebratory Book},
pages = {631--651},
organization = {John Wiley & Sons, Inc. Hoboken, NJ, USA},
keywords = {},
pubstate = {published},
tppubtype = {inproceedings}
}
|
NHC-capped cyclodextrins (ICyDs): Insulated metal complexes, commutable multicoordination sphere, and cavity-dependent catalysis Article de journal M Guitet; P Zhang; F Marcelo; C Tugny; J Jiménez-Barbero; O Buriez; C Amatore; V Mouriès-Mansuy; J -P Goddard; L Fensterbank; Y Zhang; S Roland; M Ménand; M Sollogoub Angewandte Chemie - International Edition, 52 (28), p. 7213–7218, 2013. @article{Guitet:2013,
title = {NHC-capped cyclodextrins (ICyDs): Insulated metal complexes, commutable multicoordination sphere, and cavity-dependent catalysis},
author = {M Guitet and P Zhang and F Marcelo and C Tugny and J Jim\'{e}nez-Barbero and O Buriez and C Amatore and V Mouri\`{e}s-Mansuy and J -P Goddard and L Fensterbank and Y Zhang and S Roland and M M\'{e}nand and M Sollogoub},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84880180264&doi=10.1002%2fanie.201301225&partnerID=40&md5=35bafe7534b6206686defb64d4d4e698},
doi = {10.1002/anie.201301225},
year = {2013},
date = {2013-01-01},
journal = {Angewandte Chemie - International Edition},
volume = {52},
number = {28},
pages = {7213--7218},
abstract = {Don't slam the door! Cyclodextrins capped with an N-heterocyclic carbene (ICyDs) entrapped metal ions within their cavity through a novel set of interactions, including X×××π, which enabled the cavity to be closed by ligand exchange (see scheme; Bn=benzyl). Although insulated from an electrode, the deeply buried metal ions retained catalytic activity. The cavity influenced the regio- and stereochemical outcome of the catalyzed reactions. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Don't slam the door! Cyclodextrins capped with an N-heterocyclic carbene (ICyDs) entrapped metal ions within their cavity through a novel set of interactions, including X×××π, which enabled the cavity to be closed by ligand exchange (see scheme; Bn=benzyl). Although insulated from an electrode, the deeply buried metal ions retained catalytic activity. The cavity influenced the regio- and stereochemical outcome of the catalyzed reactions. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. |
Surface grafting of a $pi$-conjugated amino-ferrocifen drug Article de journal Olivier Buriez; Fetah I Podvorica; Anouk Galtayries; Eric Labbé; Siden Top; Anne Vessi`eres; Gérard Jaouen; Catherine Combellas; Christian Amatore Journal of Electroanalytical Chemistry, 699 , p. 21–27, 2013. @article{buriez2013surface,
title = {Surface grafting of a $pi$-conjugated amino-ferrocifen drug},
author = {Olivier Buriez and Fetah I Podvorica and Anouk Galtayries and Eric Labb\'{e} and Siden Top and Anne Vessi{`e}res and G\'{e}rard Jaouen and Catherine Combellas and Christian Amatore},
year = {2013},
date = {2013-01-01},
journal = {Journal of Electroanalytical Chemistry},
volume = {699},
pages = {21--27},
publisher = {Elsevier},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
|
Surface grafting of a π-conjugated amino-ferrocifen drug Article de journal O Buriez; F I Podvorica; A Galtayries; E Labbé; S Top; A Vessières; G Jaouen; C Combellas; C Amatore Journal of Electroanalytical Chemistry, 699 , p. 21–27, 2013. @article{Buriez:2013,
title = {Surface grafting of a π-conjugated amino-ferrocifen drug},
author = {O Buriez and F I Podvorica and A Galtayries and E Labb\'{e} and S Top and A Vessi\`{e}res and G Jaouen and C Combellas and C Amatore},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84877353375&doi=10.1016%2fj.jelechem.2013.04.004&partnerID=40&md5=cc8f92b1f9773aaf470dc72898d53827},
doi = {10.1016/j.jelechem.2013.04.004},
year = {2013},
date = {2013-01-01},
journal = {Journal of Electroanalytical Chemistry},
volume = {699},
pages = {21--27},
abstract = {The electrochemical grafting of a π-conjugated amino-ferrocifen complex (1) at gold surfaces may be achieved through the direct electrochemical oxidation of the amino group (+0.9 V/SCE) but is prone to proceed also indirectly through the oxidation of the ferrocene moiety (+0.45 V). The modification and characterization of the gold electrode surfaces are demonstrated by cyclic voltammetry, ellipsometry, Infra-Red Reflection- Absorption Spectroscopy (IRRAS), Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS), and X-ray Photoelectron Spectroscopy (XPS). Combination of these techniques clearly demonstrates that (1) is covalently attached to the gold surfaces via an AuNH bond. The crucial role played by the electrogenerated aminyl radical in the grafting process is highlighted. This transient species, which is responsible for the covalent grafting of (1) onto the gold surface was also found able to react with the amino-ferrocifen parent complex to form multilayers. This detailed characterization of the grafted electrode surface finally brings insight into the overall mechanistic frame related to the grafting of conjugated amino compounds and, consequently, allowing establishing definitively the occurrence of the intramolecular redox catalysis process which is key to their cytotoxic properties against cancer cells. © 2013 Elsevier Inc. All rights reserved.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The electrochemical grafting of a π-conjugated amino-ferrocifen complex (1) at gold surfaces may be achieved through the direct electrochemical oxidation of the amino group (+0.9 V/SCE) but is prone to proceed also indirectly through the oxidation of the ferrocene moiety (+0.45 V). The modification and characterization of the gold electrode surfaces are demonstrated by cyclic voltammetry, ellipsometry, Infra-Red Reflection- Absorption Spectroscopy (IRRAS), Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS), and X-ray Photoelectron Spectroscopy (XPS). Combination of these techniques clearly demonstrates that (1) is covalently attached to the gold surfaces via an AuNH bond. The crucial role played by the electrogenerated aminyl radical in the grafting process is highlighted. This transient species, which is responsible for the covalent grafting of (1) onto the gold surface was also found able to react with the amino-ferrocifen parent complex to form multilayers. This detailed characterization of the grafted electrode surface finally brings insight into the overall mechanistic frame related to the grafting of conjugated amino compounds and, consequently, allowing establishing definitively the occurrence of the intramolecular redox catalysis process which is key to their cytotoxic properties against cancer cells. © 2013 Elsevier Inc. All rights reserved. |
Synthesis, characterization, and antiproliferative activities of novel ferrocenophanic suberamides against human triple-negative MDA-MB-231 and hormone-dependent MCF-7 breast cancer cells Article de journal J D J Cázares-Marinero; O Buriez; E Labbé; S Top; C Amatore; G Jaouen Organometallics, 32 (20), p. 5926–5934, 2013. @article{Cazares-Marinero:2013,
title = {Synthesis, characterization, and antiproliferative activities of novel ferrocenophanic suberamides against human triple-negative MDA-MB-231 and hormone-dependent MCF-7 breast cancer cells},
author = {J D J C\'{a}zares-Marinero and O Buriez and E Labb\'{e} and S Top and C Amatore and G Jaouen},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84887042245&doi=10.1021%2fom400490a&partnerID=40&md5=efad7ad74b52eb66a59d23ca2a8a9b3e},
doi = {10.1021/om400490a},
year = {2013},
date = {2013-01-01},
journal = {Organometallics},
volume = {32},
number = {20},
pages = {5926--5934},
abstract = {We report the synthesis and characterization of a new family of organometallic suberamides with strong antiproliferative activities against triple-negative MDA-MB-231 breast cancer cell lines with IC50 values ranging from 0.84 to 0.94 μM. Similar studies on hormone-dependent MCF-7 breast cancer cells were also carried out, revealing the positive effect of the ferrocenophanic moiety on disubstituted ferrocene-1,1′-diyl derivatives versus their monosubstituted ferrocenyl analogues. Cyclic voltammetry analysis showed no substantial differences between ferrocenic and ferrocenophanic suberamides in the absence or presence of a base. However, similar studies performed on related compounds strongly suggest that ferrocenophanic and ferrocenic complexes do not undergo the same redox activation patterns. The electrochemical behavior seems to be in agreement with the antiproliferative activity of this type of organometallic compound. © 2013 American Chemical Society.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
We report the synthesis and characterization of a new family of organometallic suberamides with strong antiproliferative activities against triple-negative MDA-MB-231 breast cancer cell lines with IC50 values ranging from 0.84 to 0.94 μM. Similar studies on hormone-dependent MCF-7 breast cancer cells were also carried out, revealing the positive effect of the ferrocenophanic moiety on disubstituted ferrocene-1,1′-diyl derivatives versus their monosubstituted ferrocenyl analogues. Cyclic voltammetry analysis showed no substantial differences between ferrocenic and ferrocenophanic suberamides in the absence or presence of a base. However, similar studies performed on related compounds strongly suggest that ferrocenophanic and ferrocenic complexes do not undergo the same redox activation patterns. The electrochemical behavior seems to be in agreement with the antiproliferative activity of this type of organometallic compound. © 2013 American Chemical Society. |
The effect of protic electron donor aromatic substituents on ferrocenic and [3] ferrocenophanic anilines and anilides: Some aspects of structure--activity relationship studies on organometallic compounds with strong antiproliferative effects Article de journal José de Jes'us Cázares-Marinero; Eric Labbé; Siden Top; Olivier Buriez; Christian Amatore; Gérard Jaouen Journal of Organometallic Chemistry, 744 , p. 92–100, 2013. @article{de2013effect,
title = {The effect of protic electron donor aromatic substituents on ferrocenic and [3] ferrocenophanic anilines and anilides: Some aspects of structure--activity relationship studies on organometallic compounds with strong antiproliferative effects},
author = {Jos\'{e} de Jes{'u}s C\'{a}zares-Marinero and Eric Labb\'{e} and Siden Top and Olivier Buriez and Christian Amatore and G\'{e}rard Jaouen},
year = {2013},
date = {2013-01-01},
journal = {Journal of Organometallic Chemistry},
volume = {744},
pages = {92--100},
publisher = {Elsevier},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
|
The effect of protic electron donor aromatic substituents on ferrocenic and [3]ferrocenophanic anilines and anilides: Some aspects of structureeactivity relationship studies on organometallic compounds with strong antiproliferative effects Article de journal J De Jesús Cázares-Marinero; E Labbé; S Top; O Buriez; C Amatore; G Jaouen Journal of Organometallic Chemistry, 744 , p. 92–100, 2013. @article{DeJesusCazares-Marinero:2013,
title = {The effect of protic electron donor aromatic substituents on ferrocenic and [3]ferrocenophanic anilines and anilides: Some aspects of structureeactivity relationship studies on organometallic compounds with strong antiproliferative effects},
author = {J De Jes\'{u}s C\'{a}zares-Marinero and E Labb\'{e} and S Top and O Buriez and C Amatore and G Jaouen},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84884534415&doi=10.1016%2fj.jorganchem.2013.05.047&partnerID=40&md5=8eb52ab8222684eaee90937ebd7e591c},
doi = {10.1016/j.jorganchem.2013.05.047},
year = {2013},
date = {2013-01-01},
journal = {Journal of Organometallic Chemistry},
volume = {744},
pages = {92--100},
abstract = {A new family of nitrogenous derivatives is synthesized, characterized and evaluated for the investigation of the impact of some structural motifs such as functionalization and conjugation on the antiproliferative activity of ferrocenic complexes against cancer cells. These compounds are 4,40-([3]ferrocenophan-1-ylidenemethylene)dianilides and tetramethylated dianilines derived from Michler's ketone. An alternative McMurry direct heterocoupling method for 4,40-([3]ferrocenophan-1-ylidenemethylene)dianiline synthesis is described and electrochemical studies are also discussed. © 2013 Elsevier B.V. All rights reserved.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
A new family of nitrogenous derivatives is synthesized, characterized and evaluated for the investigation of the impact of some structural motifs such as functionalization and conjugation on the antiproliferative activity of ferrocenic complexes against cancer cells. These compounds are 4,40-([3]ferrocenophan-1-ylidenemethylene)dianilides and tetramethylated dianilines derived from Michler's ketone. An alternative McMurry direct heterocoupling method for 4,40-([3]ferrocenophan-1-ylidenemethylene)dianiline synthesis is described and electrochemical studies are also discussed. © 2013 Elsevier B.V. All rights reserved. |
2012
|
Deciphering the activation sequence of ferrociphenol anticancer drug candidates Article de journal P Messina; E Labbé; O Buriez; E A Hillard; A Vessières; D Hamels; S Top; G Jaouen; Y M Frapart; D Mansuy; C Amatore Chemistry - A European Journal, 18 (21), p. 6581–6587, 2012. @article{Messina:2012,
title = {Deciphering the activation sequence of ferrociphenol anticancer drug candidates},
author = {P Messina and E Labb\'{e} and O Buriez and E A Hillard and A Vessi\`{e}res and D Hamels and S Top and G Jaouen and Y M Frapart and D Mansuy and C Amatore},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84861159405&doi=10.1002%2fchem.201103378&partnerID=40&md5=bf764a18b4bd832d2149e1a5cbc90875},
doi = {10.1002/chem.201103378},
year = {2012},
date = {2012-01-01},
journal = {Chemistry - A European Journal},
volume = {18},
number = {21},
pages = {6581--6587},
abstract = {The complete oxidation sequence of a model for ferrociphenols, a new class of anticancer drug candidate, is reported. Cyclic voltammetry was used to monitor the formation of oxidation intermediates on different timescales, thereby allowing the electrochemical characterization of both the short-lived and stable species obtained from the successive electron-transfer and deprotonation steps. The electrochemical preparation of the ferrocenium intermediate enabled a stepwise voltammetric determination of the stable oxidation compounds obtained upon addition of a base as well as the electron stoichiometry observed for the overall oxidation process. A mechanism has been established from the electrochemical data, which involves a base-promoted intramolecular electron transfer between the phenol and the ferrocenium cation. The resulting species is further oxidized then deprotonated to yield a stable quinone methide. To further characterize the transient species successively formed during the two-electron oxidation of the ferrociphenol to its quinone methide, EPR was used to monitor the fate of the paramagnetic species generated upon addition of imidazole to the electrogenerated ferrocenium. The study revealed the passage from an iron-centered to a carbon-centered radical, which is then oxidized to yield the quinone methide, namely, the species that interacts with proteins and so forth under biological conditions. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The complete oxidation sequence of a model for ferrociphenols, a new class of anticancer drug candidate, is reported. Cyclic voltammetry was used to monitor the formation of oxidation intermediates on different timescales, thereby allowing the electrochemical characterization of both the short-lived and stable species obtained from the successive electron-transfer and deprotonation steps. The electrochemical preparation of the ferrocenium intermediate enabled a stepwise voltammetric determination of the stable oxidation compounds obtained upon addition of a base as well as the electron stoichiometry observed for the overall oxidation process. A mechanism has been established from the electrochemical data, which involves a base-promoted intramolecular electron transfer between the phenol and the ferrocenium cation. The resulting species is further oxidized then deprotonated to yield a stable quinone methide. To further characterize the transient species successively formed during the two-electron oxidation of the ferrociphenol to its quinone methide, EPR was used to monitor the fate of the paramagnetic species generated upon addition of imidazole to the electrogenerated ferrocenium. The study revealed the passage from an iron-centered to a carbon-centered radical, which is then oxidized to yield the quinone methide, namely, the species that interacts with proteins and so forth under biological conditions. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. |
Deciphering the activation sequence of ferrociphenol anticancer drug candidates Article de journal Pierluca Messina; Eric Labbé; Olivier Buriez; Elizabeth A Hillard; Anne Vessi`eres; Didier Hamels; Siden Top; Gérard Jaouen; Yves Michel Frapart; Daniel Mansuy; others Chemistry--A European Journal, 18 (21), p. 6581–6587, 2012. @article{messina2012deciphering,
title = {Deciphering the activation sequence of ferrociphenol anticancer drug candidates},
author = {Pierluca Messina and Eric Labb\'{e} and Olivier Buriez and Elizabeth A Hillard and Anne Vessi{`e}res and Didier Hamels and Siden Top and G\'{e}rard Jaouen and Yves Michel Frapart and Daniel Mansuy and others},
year = {2012},
date = {2012-01-01},
journal = {Chemistry--A European Journal},
volume = {18},
number = {21},
pages = {6581--6587},
publisher = {WILEY-VCH Verlag Weinheim},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
|
Direct electrochemical reduction of organic halide droplets dispersed in water Article de journal E Deunf; E Labbé; J N Verpeaux; O Buriez; C Amatore RSC Advances, 2 (12), p. 5398–5402, 2012. @article{Deunf:2012,
title = {Direct electrochemical reduction of organic halide droplets dispersed in water},
author = {E Deunf and E Labb\'{e} and J N Verpeaux and O Buriez and C Amatore},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84893242167&doi=10.1039%2fc2ra20215h&partnerID=40&md5=0fb6823ae35567936f7b5119862facae},
doi = {10.1039/c2ra20215h},
year = {2012},
date = {2012-01-01},
journal = {RSC Advances},
volume = {2},
number = {12},
pages = {5398--5402},
abstract = {The direct electroreductive homocoupling of benzyl bromide has been efficiently achieved using water as the solvent. This process does not involve any organic co-solvent, transition metal catalyst, oil, surfactants, but only a cheap and non-toxic supporting electrolyte (KCl). Benzyl bromide droplets dispersed in water were reduced at a low current density, in an undivided cell fitted with a sacrificial aluminum anode. Various cathode materials have been tested (Ni, Pt, C, Ag) to favor organic halide reduction versus hydrogen evolution. Moreover, it was shown that the presence of aluminum cations generated by the oxidation of the anode played a crucial role in the efficiency of the electrochemical reduction step. Surprisingly, this property was exalted in acidic solutions (pH = 1). Under such acidic conditions, both bibenzyl proportion and faradaic yields were considerably improved. The electrochemical activation of energetically stronger C-X bonds such as those encountered in benzyl chloride (Csp3-Cl) or ethyl 4-iodobenzoate (Csp2-I) could be also achieved in water though resulted in lower faradaic yields. From a mechanistic point of view, both the faradaic yields and the product distribution obtained under various conditions suggested the occurrence of a radical coupling pathway occurring within the organic droplets or at their surface. © 2012 The Royal Society of Chemistry.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The direct electroreductive homocoupling of benzyl bromide has been efficiently achieved using water as the solvent. This process does not involve any organic co-solvent, transition metal catalyst, oil, surfactants, but only a cheap and non-toxic supporting electrolyte (KCl). Benzyl bromide droplets dispersed in water were reduced at a low current density, in an undivided cell fitted with a sacrificial aluminum anode. Various cathode materials have been tested (Ni, Pt, C, Ag) to favor organic halide reduction versus hydrogen evolution. Moreover, it was shown that the presence of aluminum cations generated by the oxidation of the anode played a crucial role in the efficiency of the electrochemical reduction step. Surprisingly, this property was exalted in acidic solutions (pH = 1). Under such acidic conditions, both bibenzyl proportion and faradaic yields were considerably improved. The electrochemical activation of energetically stronger C-X bonds such as those encountered in benzyl chloride (Csp3-Cl) or ethyl 4-iodobenzoate (Csp2-I) could be also achieved in water though resulted in lower faradaic yields. From a mechanistic point of view, both the faradaic yields and the product distribution obtained under various conditions suggested the occurrence of a radical coupling pathway occurring within the organic droplets or at their surface. © 2012 The Royal Society of Chemistry. |