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Direct Reversible Decarboxylation from Stable Organic Acids in Solution

preprint
submitted on 25.02.2020 and posted on 26.02.2020 by Duanyang Kong, Patrick Moon, Erica K. J. Lui, Odey Bsharat, Rylan Lundgren
Many classical and emerging methodologies in organic chemistry rely on carbon dioxide extrusion to generate reactive intermediates for subsequent bond-­forming events. Synthetic reactions that involve the microscopic reverse, the carboxylation of reactive intermediates such as organometallic nucleophiles, occur under vastly different reaction conditions. We found that under appropriate conditions chemically stable C(sp3) carboxylates undergo rapid, uncatalyzed reversible decarboxylation in solution. The decarboxylation/carboxylation process occurs through the generation and trapping of otherwise undetectable carbanion intermediates that are largely resistant to protodecarboxylation in the presence of Brønsted acids or to trapping by external electrophiles. Isotopically labelled carboxylic acids, including drug molecules and valuable synthetic intermediates, can be prepared in high chemical and isotopic yield by simply supplying an atmosphere of 13CO2 to carboxylate salts in polar aprotic solvents. Our results indicate that the reversibility of decarboxylation from organic acids should be taken into consideration when designing and executing decarboxylative functionalization processes.

History

Email Address of Submitting Author

rylan.lundgren@ualberta.ca

Institution

University of Alberta

Country

Canada

ORCID For Submitting Author

0000-0002-7760-6946

Declaration of Conflict of Interest

No conflict of interest

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