Exploration of thioglycosides in photoinduced desulfurative cross-coupling reactions
Bibliographic record
Abstract
Thioglycosides have been a mainstay of O-glycosylation chemistry. Here we demonstrate that under mild photochemical conditions, readily synthesized bench-stable electron poor thioglycosides are also useful C-glycoside precursors, undergoing desulfurative glycosyl radical generation. Two complementary classes thioglycosides are described. The glycosyl dithioimidocarbonates, undergo radical coupling in the presence of 4CzIPN, a weak acid and Hantzsch ester, under blue light illumination. Alternatively, 4-cyanotetrafluorophenyl or 4-tetrafluropyridyl thioglycosides can be used to generate glycosyl radicals in the presence of a base and Hantzsch ester under blue light irradiation in a catalyst-free approach. These radicals perform well in Geise-like reactions to yield C-glycosides with high stereoselectivity. Furthermore, related thioethers bearing 4-cyanotetrafluorophenyl groups are also potent radical precursors.
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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 | 0.001 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| 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 | 0.001 |
| Research integrity | 0.001 | 0.001 |
| 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 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".