Many classical and emerging methodologies in organic chemistry rely on carbon dioxide (CO) extrusion to generate reactive intermediates for bond-forming events. Synthetic reactions that involve the microscopic reverse-the carboxylation of reactive intermediates-have conventionally been undertaken using very different conditions. We report that chemically stable C(sp) carboxylates, such as arylacetic acids and malonate half-esters, undergo uncatalyzed reversible decarboxylation in dimethylformamide solution. Decarboxylation-carboxylation occurs with substrates resistant to protodecarboxylation by Brønsted acids under otherwise identical conditions. Isotopically labeled carboxylic acids can be prepared in high chemical and isotopic yield by simply supplying an atmosphere of CO to carboxylate salts in polar aprotic solvents. An understanding of carboxylate reactivity in solution enables conditions for the trapping of aldehydes, ketones, and α,β-unsaturated esters.

Download full-text PDF

Source
http://dx.doi.org/10.1126/science.abb4129DOI Listing

Publication Analysis

Top Keywords

reversible decarboxylation
8
dimethylformamide solution
8
direct reversible
4
decarboxylation stable
4
stable organic
4
acids
4
organic acids
4
acids dimethylformamide
4
solution classical
4
classical emerging
4

Similar Publications

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!