Direct Reversible Decarboxylation from Stable Organic Acids in Solution
Bibliographic record
Abstract
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.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.002 | 0.001 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".