Bibliographic record
Abstract
Abstract Radical substitution on tetrasulfides is demonstrated to be a highly effective means to prepare unsymmetric disulfides. Alkyl and aryl radicals generated thermally or photochemically underwent substitution on readily prepared dialkyl, diaryl, and diacyl tetrasulfides to yield the corresponding disulfides in good to excellent yields. Classic and contemporary thermal and photochemical radical sources could be employed; while photoredox catalysis approaches led to either oxidation or reduction of the tetrasulfide, energy transfer photocatalysis was particularly useful. The success of the approach is driven by the thermodynamic stability of the perthiyl radicals formed upon substitution on the tetrasulfide; they simply combine under the reaction conditions to provide the starting tetrasulfide. Competition kinetic experiments reveal that alkyl radical substitution on tetrasulfides is a rapid reaction (6 × 105 M–1 s–1) that is enhanced at least 6-fold upon moving from dialkyl tetrasulfide to diacyl tetrasulfide due to favorable polar effects. This unique and versatile reaction enables introduction of disulfide moieties from a variety of radical precursors and straightforward access to hydropersulfides.
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 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 | 0.000 |
| 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".