Hydrocoupling, cathodic

Mixed hydrocoupling reactions in dimethylfonnamide, containing chlorotri-methylsilane, at a lead cathode with tetrathylammonium toluene-4-sulphonate electrolyte. The aldehyde or ketone is in five-fold excess. Ref [135]. 

There are other processes besides the production of piperidine that occur during cathodic transformations of pyridine. Depending on conditions, dimers, crossed hydrocoupling products, or polymers can be formed these other products can also have a partially or fully reduced ring. 

Chlorotrimethylsilane (CTMS) has been shown to promote various cathodic hydrocoupling reactions. Thus, cathodic reduction of a mixture of carbonyl compounds and activated olefins122 or imines123 in the presence of CTMS provides carbon-carbon cross-ed-coupling products efficiently. The cathodic reduction of aromatic esters and an amide to produce aldehydes was also promoted in the presence of CTMS124. 

The reaction mechanism for cathodic hydrocoupling of acrylonitrile has been extensively investigated by many researchers and it has been establishedas shown in Scheme 1 [2-4]. Firstly, an anion radical of acrylonitrileis generated by the first one-electron transfer to an acrylonitrile molecule from cathode. An anion radical of acrylonitrilecombines with an unreacted acrylonitrilemolecule. Finally, the... 

Cathodk Hydrocoupling of Acrylonitrile (Electrosynthesis of Adiponitrile), Scheme 1 Mechanism for the cathodic reduction of acrylonitrile to adiponitrile... 

Brown,O.R., Lister,K. Reduction of acetone and its hydrocoupling with acrylonitrile in aqueous sulfuric acid solution at a mercury cathode. Discussions Faraday Soc. 45,106 (1968). 

Cathodic crc ed hydrocoupling ofacetone with acrylonitrile and maleic acid. Electrochim. Acta 13, 613 (1968). 

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