Biomimetic Monoacylation of Diols in Water. Lanthanide-Promoted Reactions of Methyl Benzoyl Phosphate
Bibliographic record
Abstract
The direct monoacylation of diols by acyl phosphate monoesters in water is a biomimetic analogy to the enzymic aminoacylation of tRNA by aminoacyl adenylates. Without catalysis, acyl phosphate monoesters react rapidly with amines but very slowly with water and alcohols. Lanthanide ions dramatically and selectively facilitate the base-catalyzed monoacylation of diols in water by methyl benzoyl phosphate (MBP), a typical acyl phosphate monoester, in neutral solutions where reactive amines are protonated and unreactive. The reaction patterns and reactivity of various diols with MBP in the presence of lanthanides are consistent with a mechanism that involves internal addition from the conjugate base of the bis-bidentate complex of the lanthanide with the diol and MBP. The method is also applicable to reactions of nucleosides as evidenced by the selective monoacylation of the 2'- or 3'-hydroxyl group of adenosine, without reaction of the 5'-hydroxyl group or the 6-amino group. Analogues of adenosine without the diol are unreactive. This suggests that the method will selectively monoacylate the hydroxyl groups at the unique diol in tRNA that forms the 3'-terminus.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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) | 0.001 | 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 | 0.001 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.002 | 0.001 |
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".