Photocatalytic C–S Bond Formation Using <i>N</i>-Thiophthalimide and <i>N-</i>Perthiophthalimide Derivatives
Bibliographic record
Abstract
Unsymmetric disulfides are shown to be accessed directly from carboxylic acids or trifluoroborate salts by using N -perthiophthalimide derivatives (Harpp reagents) under photoredox catalysis. While this would appear to involve homolytic substitution of alkyl radicals on the Harpp reagents, the formation of the high-energy phthalimidyl radical renders this reaction prohibitively endergonic. Instead, computations and experiments suggest that the Harpp reagents are reduced in situ to form perthiyl radicals that dimerize to tetrasulfides (RSSSSR), which have previously been demonstrated to undergo radical substitution to give disulfides. Given these results, examples of previously reported radical sulfurations using N -thiophthalimide reagents under photoredox catalysis were investigated. Our results suggest that these reactions are likely to proceed via in situ formation of the corresponding disulfide as the sulfuration reagent rather than direct substitution on the N -thiophthalimide. The implications of these findings for the use of phthalimide (and related) derivatives in photoredox-catalyzed reactions are discussed.
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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 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| 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 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".