Electroreductive Coupling Research Articles

Scaling out of electrolyte free electrosynthesis in a micro-gap flow cell

The electro-reductive coupling of activated olefins and benzyl bromide derivatives has been selected to compare the performance of single and multiple channel (scaled-out) micro-gap electrochemical flow reactors. Two working electrode configurations were evaluated; in the first a single set of electrodes was used in conjunction with a multiple flow manifold to give two and four separate flow channels; in the second independent electrodes were used within the same flow manifold. Problems with shunt currents and Joule heating in the first configuration meant that only the second configuration was reliable, giving results comparable to those obtained for the single flow cell. Excellent yields of the coupling products such as 2-benzyl-succinic acid dimethyl ester and derivatives were obtained. This demonstrates micro reactor scale-out for unsupported electrosyntheses.

Electro Organic Synthesis Utilizing Mg Electrodes (II) - Novel Synthesis of Symmetric Azobenzenes from Nitrobenzenes -

On the way to study electro organic synthesis (EOS) utilizing alternating Mg electrodes, a novel synthetic route from the nitrobenzenes to symmetric azobenzenes was discovered in our laboratory. The brief review about EOS was introduced by us. The EOS is expected to be an important organic synthetic tool in future because of its diverse application in industry in addition to compatibility with green chemistry. In the previous paper, we reported the optimized reaction conditions for the electro reductive coupling of aromatic halides: Mg rod for both of anode and cathode under a constant current, LiClO4 as a electrolyte, THF or glyme 7 as a solvent. We have tried to extend EOS to other functional groups. Since nitrobenzenes were readily reduced under the various mild reaction conditions, we exposed several nitrobenzenes under EOS reaction conditions. Our reaction conditions were Mg for anode and cathode, LiClO4, THF, room temperature under a constant current (current density = 42 mA/cm). The currents of anode and cathode were alternated at an interval of 30 seconds in order to minimize the consumption of the metal. The reaction mixture was carefully monitored by TLC and then worked up when nitrobenzene 1 was completely disappeared. The new spot was isolated and characterized fully by TLC and spectroscopic methods with an authentic sample. To our surprise, it was azobenzene 2 instead of aniline 3 based on the previously reported paper. The optimized yield of 2 was 87.6 % with no trace of the desired aniline 3. The amount of Mg consumed during the reaction was less then 5.0% for every attempt (eq. 1).

Epoxide Formation by Indirect Electroreductive Coupling Between Aldehydes or Ketones and Activated gem‐Dichloro Compounds.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Epoxide Formation by Indirect Electroreductive Coupling between Aldehydes or Ketones and Activatedgem-Dichloro Compounds

Epoxides are prepared by indirect electroreductive coupling of carbonyl compounds (aldehydes or ketones) and activated gem-dichloro compounds. This process is more efficient with aryl ketones than with aryl aldehydes. Though yields are only moderate, this method offers the valuable advantage of avoiding the use of strong bases or peroxides.

Room‐Temperature Ionic Liquids as New Solvents for Organic Electrosynthesis. The First Examples of Direct of Nickel‐Catalyzed Electroreductive Coupling Involving Organic Halides.

ChemInformVolume 34, Issue 41 Preparative Organic Chemistry Room-Temperature Ionic Liquids as New Solvents for Organic Electrosynthesis. The First Examples of Direct of Nickel-Catalyzed Electroreductive Coupling Involving Organic Halides. Rachid Barhdadi, Rachid Barhdadi Lab. Electrochim., Catal. Synth. Org., CNRS, Univ. Paris 12, F-94320 Thiais, Fr.Search for more papers by this authorCoralie Courtinard, Coralie Courtinard Lab. Electrochim., Catal. Synth. Org., CNRS, Univ. Paris 12, F-94320 Thiais, Fr.Search for more papers by this authorJean Yves Nedelec, Jean Yves Nedelec Lab. Electrochim., Catal. Synth. Org., CNRS, Univ. Paris 12, F-94320 Thiais, Fr.Search for more papers by this authorMichel Troupel, Michel Troupel Lab. Electrochim., Catal. Synth. Org., CNRS, Univ. Paris 12, F-94320 Thiais, Fr.Search for more papers by this author Rachid Barhdadi, Rachid Barhdadi Lab. Electrochim., Catal. Synth. Org., CNRS, Univ. Paris 12, F-94320 Thiais, Fr.Search for more papers by this authorCoralie Courtinard, Coralie Courtinard Lab. Electrochim., Catal. Synth. Org., CNRS, Univ. Paris 12, F-94320 Thiais, Fr.Search for more papers by this authorJean Yves Nedelec, Jean Yves Nedelec Lab. Electrochim., Catal. Synth. Org., CNRS, Univ. Paris 12, F-94320 Thiais, Fr.Search for more papers by this authorMichel Troupel, Michel Troupel Lab. Electrochim., Catal. Synth. Org., CNRS, Univ. Paris 12, F-94320 Thiais, Fr.Search for more papers by this author First published: 19 September 2003 https://doi.org/10.1002/chin.200341056Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume34, Issue41October 14, 2003 RelatedInformation

Room-temperature ionic liquids as new solvents for organic electrosynthesis. The first examples of direct or nickel-catalysed electroreductive coupling involving organic halides.

Direct or Ni-catalysed electroreductive homocouplings of organic halides and couplings of organic halides with activated olefins are efficiently conducted by constant current electrolyses in an undivided cell in room-temperature ionic liquids as the solvent-electrolyte media.

ChemInform Abstract: Cyclopropane Formation by Copper‐Catalyzed Indirect Electroreductive Coupling of Activated Olefins and Activated α,α,α‐Trichloro or gem‐Dichloro Compounds.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Cyclopropane Formation by Nickel‐Catalyzed Electroreductive Coupling of Activated Olefins and Unactivated gem‐Dibromo Compounds.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Cyclopropane Formation by Copper-Catalysed Indirect Electroreductive Coupling of Activated Olefins and Activated α,α,α-Trichloro or Gem-Dichloro Compounds

Cyclopropanes have been prepared in good yields by indirect electroreductive coupling ol activated olefins and activated α,α,α-trichloro or gem-dichloro compounds (Cl 3 CCO 2 Me, PhCCl 3 . Ph 2 CCl 2 , PhCHCl 2 ). This process,using a copper complex in catalytic amountss is convenient for the reagent couple activated olefin/ activated polyhalide, whatever the reduction potential of each reagent relative to each other. The main advantage of our electrochemical process is that it does not require the use of hazardous, toxic, or not easily prepared reagents like diazocompounds or diazirines.

Cyclopropane formation by nickel-catalysed electroreductive coupling of activated olefins and unactivated gem-dibromo compounds

Cyclopropyl derivatives have been prepared with good yields by transition-metal catalysed electroreductive coupling of activated olefins and unactivated gem-dibromo compounds. This electrolysis is characterized by the use of a Fe/Ni catalyst system, acetonitrile as the solvent and a catalytic amount of triphenylphosphine as ligand. This procedure is a good alternative to the classical preparations of cyclopropyl derivatives from activated olefins (Simmons–Smith reaction, 1,3-dipolar addition of diazomethane, 1,4-addition of phosphorus and sulfur ylides).

Parallel electrosynthesis of 1,2-diamines.

Parallel reductive hydrocoupling of aldimines was performed to generate vicinal diamines using the spatially addressable electrolysis platform (SAEP). The stainless steel cathodes and sacrificial aluminum anodes were used in this electrosynthesis methodology. Introducing a large substituent on the imino nitrogen atom efficiently controls stereoselectivity of the electroreductive coupling process. This method can now be applied to the generation of libraries of 1,2-diamines, which further expands the techniques of parallel synthesis and combinatorial electrochemistry.

Electroreductive Coupling of Aromatic Acyl Bromides to 1,2-Diketones

Abstract The direct electroreduction of aromatic acyl bromides gave aromatic 1,2-diketones. The best result was obtained using a Pb cathode in acetonitrile containing Bu4NClO4 as a supporting electrolyte. Aromatic acyl bromides substituted by an electron-donating group afforded 1,2-diketones in moderate-to-good yields, whereas acylated endiols were formed exclusively from aromatic acyl bromides substituted by an electron-withdrawing group.

Electroreductive Coupling of Organic Halides with Aldehydes Catalyzed by Nickel(0) Complex with 2,2'-Bipyridine

A method of electrosynthesis of secondary alcohols from aldehydes and organic halides under the action of nickel(0) complexes is proposed. The key stage is addition of σ-complex RNi(I)bipy (bipy is 2,2'-bipyridine) to the aldehyde group.

電極還元法による含ケイ素ポリマーの合成

The electroreduction of organochlorosilanes was carried out by using magnesium cathode and anode in a single compartment cell affording oligosilanes, polysilanes, and polycarbosilanes. The electroreductive coupling of organochlorosilanes gave the corresponding disilanes in high yield. The cross-coupling of chloroorganosilanes with dichloroorganosilanes under the same reaction conditions produced various types of oligosilanes such as trisilanes, tetrasilanes, and pentasilanes. This procedure was successfully applied to the stepwise elongation of silicon-silicon chains. The high efficiency of this electroreductive silicon-silicon bond formation reaction enabled the electroreductive synthesis of poly (alkylarylsilane) s having high molecular weight (Mn=5200-31000, Mw/Mn=1.4-1.8). The electroreductive polymerization of the dichlorosilanes bearing various types of functional groups was also carried out to afford the functionalized polysilanes. Moreover, the electroreductive polymerization of dichlorooligosilanes was successfully applied to the synthesis of sequence-ordered polysilanes. This electroreductive method was also applicable to the synthesis of poly-p- (disilanylene) phenylenes and silane-germane copolymers. The effects of electrode material, monomer concentration, amount of supplied electricity, and ultrasound were investigated in these reactions.

ChemInform Abstract: Catalysis by Nickel—2,2′‐Dipyridylamine Complexes of the Electroreductive Coupling of Aromatic Halides in Ethanol.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Catalysis by nickel-2,2′-dipyridylamine complexes of the electroreductive coupling of aromatic halides in ethanol

Nickel-2,2′-dipyridylamine complexes are efficient catalysts for achieving in pure ethanol electroreductive dimerisation of aromatic halides or arylation of activated olefins.

ChemInform Abstract: Electroorganic Chemistry. Part 155. Electroreductive Coupling of Aliphatic Amides. A Useful Method for the Synthesis of α‐Amino Ketones.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Electroreductive coupling of aliphatic amides. A useful method for the synthesis of α-amino ketones

Electroreduction of aliphatic amides (RCONMe2) with Mg electrode in the presence of chlorotrimethylsilane (TMSCI) has been found to give the coupling products [R(TMSO)CC(NMe2)R] and hydrolysis of the products affords the corresponding α-amino ketones [RCOCH(NMe2)R] in excellent yields.

ChemInform Abstract: Cyclopropane Formation by Electroreductive Coupling of Activated Olefins and gem‐Polyhalo Compounds.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Electrochemical generation of a nickel–carbonyl complex, catalyst for the electroreductive coupling of organic halides and carbon monoxide into ketones

The nickel–carbonyl complex Ni(CO)bpy is involved in the nickel-catalysed electroreductive coupling of organic halides and carbon monoxide into ketones. The active species is obtained from a stoichiometric mixture of Ni 0, 2,2′-bipyridine and CO. The electrochemical method used to generate this complex allows a good tuning of Ni 0 production versus CO dissolution. We have shown that Ni(CO)bpy results from a CO equilibrium exchange between Ni(CO) 2bpy and Nibpy.