We have developed a novel electrolytic system for Kolbe carbon-carbon coupling electrosynthesis based on the acid-base reaction between carboxylic acids as a substrate and solid-supported bases. On the basis of the electrolytic system, Kolbe electrolysis of various carboxylic acids was successfully carried out to provide the corresponding homocoupling products in moderate to excellent yields.
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http://dx.doi.org/10.1021/jo801016f | DOI Listing |
J Am Chem Soc
July 2024
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
The catalytic cross-coupling of identical or similar functional groups is a cornerstone strategy for carbon-carbon bond formation, as exemplified by renowned methods, such as olefin cross-metathesis, Kolbe electrolysis, and various cross-electrophile couplings. However, similar methodologies for coupling aldehydes─fundamental building blocks in organic synthesis─remain underdeveloped. While the benzoin-type condensation, first reported in 1832, offers a reliable route for aldehyde dimerization, the chemo- and enantioselective cross-coupling of nonidentical yet similar aldehydes remains an unsolved challenge.
View Article and Find Full Text PDFJ Am Chem Soc
January 2024
Department of Chemistry, School of Science, Kwansei Gakuin University, Sanda 669-1330, Hyogo, Japan.
Kolbe dimerization and Hofer-Moest reactions are well-investigated carboxylic acid transformations, wherein new carbon-carbon and carbon-heteroatom bonds are constructed via electrochemical decarboxylation. These transformations can be switched by choosing an electrode that allows control of the reactive intermediate, such as carbon radical or carbocation. However, the requirement of a high current density diminishes the functional group compatibility with these electrochemical reactions.
View Article and Find Full Text PDFScience
April 2023
Department of Chemistry, Scripps Research, La Jolla, CA 92037, USA.
The Kolbe reaction forms carbon-carbon bonds through electrochemical decarboxylative coupling. Despite more than a century of study, the reaction has seen limited applications owing to extremely poor chemoselectivity and reliance on precious metal electrodes. In this work, we present a simple solution to this long-standing challenge: Switching the potential waveform from classical direct current to rapid alternating polarity renders various functional groups compatible and enables the reaction on sustainable carbon-based electrodes (amorphous carbon).
View Article and Find Full Text PDFBeilstein J Org Chem
February 2015
Manchester Metropolitan University, Faculty of Science and Engineering, School of Science and the Environment, Division of Chemistry and Environmental Science, John Dalton Building, Chester Street, Manchester, M1 5GD, UK.
N-acyliminium ions are useful reactive synthetic intermediates in a variety of important carbon-carbon bond forming and cyclisation strategies in organic chemistry. The advent of an electrochemical anodic oxidation of unfunctionalised amides, more commonly known as the Shono oxidation, has provided a complementary route to the C-H activation of low reactivity intermediates. In this article, containing over 100 references, we highlight the development of the Shono-type oxidations from the original direct electrolysis methods, to the use of electroauxiliaries before arriving at indirect electrolysis methodologies.
View Article and Find Full Text PDFJ Org Chem
September 2008
Department of Electronic Chemistry, Tokyo Institute of Technology, Yokohama 226-8502, Japan.
We have developed a novel electrolytic system for Kolbe carbon-carbon coupling electrosynthesis based on the acid-base reaction between carboxylic acids as a substrate and solid-supported bases. On the basis of the electrolytic system, Kolbe electrolysis of various carboxylic acids was successfully carried out to provide the corresponding homocoupling products in moderate to excellent yields.
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