An unexpected elimination product leads to 4-alkyl-4-deoxy-4-<i>epi</i>-sialic acid derivatives
Bibliographic record
Abstract
A useful, unexpected β,γ-unsaturated-α-keto ester (ethyl (E)-5-acetamido-3,4,5-trideoxy-6,7:8,9-di-O- isopropylidene-D-manno-non-3-en-2-ulosonate 5) was isolated in 91% yield following ozonolysis and chromatographic purification of its enoate ester precursor ethyl 5-acetamido-2,3,4,5-tetradeoxy-6,7:8,9-di-O-isopropylidene-2-methylene- 4-nitro-D-glycero-D-galacto-nononate (6). When the 4R enoate ester (ethyl 5-acetamido-2,3,4,5-tetradeoxy-6,7:8,9-di-O- isopropylidene-2-methylene-4-nitro-D-glycero-D-talo-nononate, 7) was subjected to the same conditions, enone 5 was a minor product (18%) while the major product did not eliminate HNO2 but instead cyclized to form a five-membered ring containing a hemiaminal linkage between C-2 and the amide nitrogen on C-5 (9, 70%). Conjugate addition to enone 5 opens up the potential to generate 4-substituted sialic acid derivatives, a general route to such compounds that has not been previously reported. In a preliminary investigation of such a route, diethylzinc and dimethylzinc were added to enone 5 resulting in generation of 4-alkyl-substituted cyclic hemiaminal structures 11 and 13, which could be deprotected to form 2,7-anhydrosialic acid analogues 14 and 15. These products could then be converted to peracetylated glycals 16 and 17, the 4-methyl-substituted compound 17 being finally deprotected to give a 4-methyl- substituted analogue of the glycal of sialic acid (5-acetamido-2,6-anhydro-3,4,5-trideoxy-4-methyl-D-glycero-D-talo-non-2-enonic acid 18).Key words: conjugate addition, dialkylzinc reagent, sialic acid, ozonolysis, inhibitors.
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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) | 0.000 | 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 | 0.001 |
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".