Electrolytic Reductive Coupling

Abstract

Acrylonitrile has been reductively coupled with acetone, styrene, 1,1-diphenylethylene, benzophenone, and benzaldehyde. When the reduction is carried out at the cathode voltage required for the more difficultly rather than the more easily reduced partner (a) current efficiencies for the mixed products are increased, (b) couplings which otherwise fail can occur, (c) by-product polymer formation may be suppressed, and (d) when either of two by-product hydrodimers must be accepted, the more useful one may be chosen. ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 130.88.90.140 Downloaded on 2015-03-30 to IP ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 130.88.90.140 Downloaded on 2015-03-30 to IP

Electrohydrodimerization Reactions

“…Further experiments are currently under way to uncover the nature of the difference between the reactivity of the transand c/s-isomers. In conclusion these experiments demonstrate that cross-coupling will compete with dimerization only when the ratio of the second olefin (e.g., AN) to the reduced olefin (DEF) is very large, and that cross-coupling can probably be carried out more efficiently by reducing both reactants (7).…”

“…radical anions.--To determine the extent of crosscoupling arising from a radical ion-radical ion mechanism (Eq. [7]), an examination of the DF-CN mixed system at potentials where both DF and CN undergo reduction to form their respective radical anions was undertaken.…”

“…CN was chosen because its hydrodimerization has been studied (1), because its secondorder rate constant is only eight times that of dimethyl fumarate, and because it is more difficult to reduce than dimethyl fumarate. Acrylonitrile was chosen because of its use in previous studies (4)(5)(6)(7). The mechanism and rate of dimerization of AN, however, have not been determined because the electrogenerated product reacts very quickly (9).…”

Use of Electrochemistry in the Synthesis of Heterocyclic Structures

“…Electrogenerated gem-dichloro carbanions from electrochemical reduction of trichloroacetate can undergo electrophilic attack of some reagents, such as proton, 143 α,β-unsaturated compounds, 144 and carbonyl compounds. 145,146 Nishiguchi et al reported a stereoselective and facile synthesis of 2-chloroepoxyester 412 through electroreductive cross-coupling of methyl trichloroacetate 411 with aliphatic aldehydes (Scheme 144).…”

Electrochemical CO2 Fixation to α-Methylbenzyl Bromide in Divided Cells with Nonsacrificial Anodes and Aqueous Anolytes

“…While divided cells with nonsacrificial anodes have been reported for EC of several organic substrates, 17−20 for halides any mentions are limited to unsuccessful attempts. 21,22 Despite EC reactions of organic halides with Mg or Al anodes giving high yields of carboxylation products, their exact formation mechanism remains unclear. Electrochemical reduction of R−X in the presence of CO 2 is a three-step process: (1) halide reduction to a radical R • , (2) R • reduction to the corresponding anion R − , and (3) nucleophilic addition of R − to CO 2 with a formation of carboxylate anion.…”