TiO<sub>2</sub>-photocatalyzed reactions of some benzylic donors
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Bibliographic record
Abstract
TiO 2 -photocatalyzed oxidation of toluene (1a), benzyltrimethylsilane (1b), and 4-methoxybenzyltrimethylsilane (1c) has been carried out in acetonitrile under oxygen, under nitrogen, and in the presence of electrophilic alkenes under various conditions (using Ag 2 SO 4 as electron acceptor, adding 2.5% H 2 O, changing solvent to CH 2 Cl 2 ). Benzyl radicals, formed via electron transfer and fragmentation, are trapped. A good material balance is often obtained. The overall efficiency of the process depends on the donor E ox , on the rate of fragmentation of the radical cation, and on the acceptor present (Ag + is an efficient oxidant, an electrophilic alkene a poor one, O 2 is intermediate). With ring-unsubstituted benzyl derivatives 1a and 1b, oxidative fragmentation occurs mainly close to the catalyst surface. The benzyl radicals form at a high local concentration and give benzaldehyde under O 2 , bibenzyl under N 2 and dibenzylated derivatives by attack on the alkenes (acrylonitrile, fumaronitrile, maleic acid). In this case, using CH 2 Cl 2 O 2 enhances the yield of benzaldehyde. With methoxylated 1c, however, the radical cation migrates into the solution before fragmentation and, therefore, the free benzyl radical is formed. This radical in part is oxidized to the cation, giving a considerable amount of benzylacetamide (or of the alcohol with water), and in part is trapped by the alkenes. The last reaction is less efficient in this case and yields monobenzyl derivatives.Key words: photocatalysis, oxidation, alkylation.
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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 | 0.000 |
| 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 it