Selective monophosphorylation of cyclic diols and polyols <i>via</i> hemiboronic acid catalysis
Why this work is in the frame
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Bibliographic record
Abstract
The phosphorylation of organic molecules is a biologically essential chemical transformation. Consequently, there is high demand for methods that allow for the direct, selective, and catalytic monophosphorylation of diols and complex polyols. Due to their ability to form reversible covalent bonds with hydroxy (-OH) groups, hemiboronic acids present the unique capacity to catalytically activate diols in a nucleophilic manner. Herein, we disclose a hemiboronic acid-catalyzed monophosphorylation protocol, amenable to a variety of acyclic and cyclic diols, along with the site-selective functionalization of polyols including saccharides. Mechanistic analyses comprising of kinetic experiments and computational investigation were performed to probe for the origin of the observed site-selectivities. We propose that the observed site-selectivity originates from a difference in calculated nucleophilicity between the diol oxygens in the lower energy epimer of the reactive complex, which also exhibits a kinetically stabilizing hydrogen bonding effect with the approaching electrophile.
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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 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| 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