Electrochemical synthesis of carboxylic acids from alkenes using various nickel-organic mediators: CO2 as C1-synthon

✍ Scribed by J. Bringmann; E. Dinjus

• Book ID: 101347583
• Publisher: John Wiley and Sons
• Year: 2001
• Tongue: English
• Weight: 84 KB
• Volume: 15
• Category: Article
• ISSN: 0268-2605
• DOI: 10.1002/1099-0739(200102)15:2<135::aid-aoc108>3.0.co;2-l

✦ Synopsis

Direct and mediated electrochemical reductive coupling reactions between alkenes and CO 2 have been studied using an undivided electrochemical cell. Propene and 1-butene were used to study the behavior of monoenes. Propene, in the absence of a mediator, yielded two main products: 2-methyl-butanedioic acid and 3butenoic acid; from 1-butene, mainly ethenylsuccinic acid and 3-pentenoic acid were generated. As a conjugated diene, 1,3-butadiene was investigated intensively. In the absence of a mediator, 1,3-butadiene was mainly dicarboxylated to give the 1,2-(2-ethenyl-succinic acid) and 1,4-addition product (3-hexene-1,6-dioic acid) and various higher coupling products. Using an NiN3 mediator the reaction between 1,3-butadiene and CO 2 resulted in a preferred generation of the 1,4-addition product: 3-hexene-1,6-dioic acid. Experiments with a Ni-(cyclam) mediator resulted in an increased concomitant generation of a monocarboxylation product: 3-pentenoic acid.