Bibliographic record
Abstract
Divided into three distinct research areas, this thesis investigates the synthetic utility of divinyl ketones as versatile substrates in the construction of novel cyclic structures. The first volume of work (Chapter 2) examines the one-pot Brønsted acid-catalysed tandem double alkylation of indole with non-symmetrical divinyl ketones. The [6,5,7] tricyclic indole products are often furnished in excellent yield, with complete regioselectivity and high levels of syn-diastereoselectivity. Optimisation, a thorough substrate investigation and initial results are all discussed within. An in-depth mechanistic study is described in Chapter 3. Experimental and computational data is utilised to elucidate the reaction pathway and help explain the high levels of regioand diastereoselectivity observed during the tandem double alkylation of indoles developed in Chapter 2. The mechanism for the annulation step is shown to proceed via a 7-endo-mode C-2 Friedel-Crafts alkylation of the indole for which the rate-determining step is believed to be the loss of C-2 the proton to regain aromaticity. The final chapter concerns the phase transfer catalysed double Michael addition of activated methylene pronucleophiles to non-symmetrical divinyl ketones. The resultant substituted cyclohexanones are constructed in high yields with broad tolerance to substrate scope. In addition, proof-of-concept levels of enantioselectivity have been obtained with the use of N-alkylated Cinchona alkaloids as chiral phase transfer catalysts. With 36% enantiomeric excess, this tandem [5C+1C] annulation is shown to be an appropriate method of furnishing enantioenriched cyclohexanones.
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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 | 0.001 | 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 | 0.001 |
| 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".