Chemoenzymatic total synthesis of <i>ent</i>-neopinone and formal total synthesis of <i>ent</i>-codeinone from β-bromoethylbenzene*
Bibliographic record
Abstract
Formal total synthesis of ent-codeinone and ent-codeine was accomplished via the total synthesis of ent-neopinone attained in 14 steps from β-bromoethylbenzene. The key steps included (i) enzymatic dihydroxylation of β-bromoethylbenzene with E. coli JM109 (pDTG601a), an organism that overexpresses toluene dioxygenase, (ii) a Heck reaction to establish C-13 stereogenic center, (iii) aldol condensation, and (iv) 1,6-conjugate addition of the ethylamino side chain to C-9. Several other modes of construction of the C-9 and C-14 centers were also investigated: Mannich cyclization, and aza-Prins reaction. The synthesis of ent-codeinone was formalized by intersecting Fukuyama’s recently published approach. Experimental and spectral data are provided for all new compounds.
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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 | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.005 | 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".