Total Synthesis of Small Molecules that Target Biological Pathways and Saccharin-based Diels Alder Reactions
Bibliographic record
Abstract
The thesis is presented in four chapters that summarizes work carried out in the laboratory of Professor Robert A. Batey at the University of Toronto from 2017 to 2022. Chapter 1, the introduction of acylation reactions (formation of N–Acyl, O–Acyl, S–Acyl bonds), common acylating reagents, and the applications of acylation reactions in organic chemistry as well as total syntheses of natural products. Chapter 2 covers the total synthesis of biological active cyclic depsipeptides chaiyaphumines A-D through different macroyclization approaches. The synthesis employs both O- and N-acylation chemistry to build amide and ester bonds. A comparison between macrolactonization and macrolactamization is made along with the effects of lanthanide triflates as additives for both methods. Chapter 3 of this thesis starts with the overview of the protein degradation pathway by the UPS and how acylations are involved in the mechanism. The total synthesis of the unusual E1 ligase inhibitor himeic acid A and analogues are described. This chemistry involves both O- and N-acylation reactions as key steps in the synthesis. Finally, chapter 4 of this thesis describes the development of a highly diastereoselective, Lewis acid catalyzed N-acyl saccharin-based Diels-Alder reaction and attempts to develop an enantioselective variant. The N-acyl saccharin containing cycloaddition products are crystalline, making their purifications very convenient. Further derivatizations of acyl saccharins to give various functional groups through nucleophilic substitution reactions are described, including transformations to ester, thioester, and amide functional groups.
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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) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.001 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.001 | 0.001 |
| Open science | 0.000 | 0.001 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.007 | 0.004 |
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".