N-Ammonium Ylide Mediators for Selective Electrochemical C–H Oxidation
Bibliographic record
Abstract
<p>The site-specific oxidation of strong C(sp3)-H bonds is of uncontested utility in organic</p><p>synthesis. From simplifying access to metabolites and late-stage diversification of lead compounds</p><p>to truncating retrosynthetic plans, there is a growing need for new reagents and methods for</p><p>achieving such a transformation in both academic and industrial circles. One main drawback of</p><p>current chemical reagents is the lack of diversity with regards to structure and reactivity that</p><p>prevent a combinatorial approach for rapid screening to be employed. In that regard, directed</p><p>evolution still holds the greatest promise for achieving complex C–H oxidations in a variety of</p><p>complex settings. Herein we present a rationally designed platform that provides a step towards</p><p>this challenge using N-ammonium ylides as electrochemically driven oxidants for site-specific,</p><p>chemoselective C(sp3)–H oxidation. By taking a first-principles approach guided by computation,</p><p>these new mediators were identified and rapidly expanded into a library using ubiquitous building</p><p>blocks and trivial synthesis techniques. The ylide-based approach to C–H oxidation exhibits</p><p>tunable selectivity that is often exclusive to this class of oxidants and can be applied to real world</p><p>problems in the agricultural and pharmaceutical sectors.</p>
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
How this classification was reachedexpand
Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.002 |
| Meta-epidemiology (narrow) | 0.000 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.001 | 0.000 |
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 teacher head, 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".