Photocatalytic C–S Bond Formation Using <i>N</i>-Thiophthalimide and <i>N-</i>Perthiophthalimide Derivatives
Why this work is in the frame
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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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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 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 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 it