Origin of Diastereoselectivity in the Tandem Oxy-Cope/Claisen/Ene Reaction: Experimental and Theoretical Studies of the Ring Inversion Mechanism
Bibliographic record
Abstract
We report herein a detailed investigation into the reaction mechanism of the oxy-Cope/Claisen/ene reaction. A series of chiral substrates was prepared, subjected to the tandem sequence, and the enantiomeric excess of the final products was evaluated. The observed conservation of enantiomeric excess was taken as evidence that the ring inversion of the intermediary enol ether does not occur. DFT calculations were used to map out the potential energy surface for the reaction and evaluate the relative energies of the ring inversions relative to those of the Claisen and ene reactions. Transition state energies thus obtained were found to support the presence of a high-energy transition state for the ring inversion of B to D provided R(1) not equal H. In addition, the calculations lent further support to the hypothesis that the selectivity of the transannular ene reaction is under Curtin-Hammett control.
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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 | 0.001 |
| 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) | 0.002 | 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 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".