Exploring the Role of Aminocatalysis in the Dearomatization and Regioselectivity of Heteroaromatic Aldehydes
Bibliographic record
Abstract
Heteroaromatic aldehydes have recently received a lot of attention as a scaffold for aminocatalytic functionalization as they allow for the construction of remote stereocenters and highly complex heterocyclic compounds. In this paper, we employ computational methods (M06-2X/cc-pVTZ//M06-2X/6-31 + G(d,p) and MP2/cc-pVTZ//M06-2X/6-31 + G(d,p)) to examine the abilities of secondary amines to activate several model heteroaromatic aldehydes by promoting loss of aromaticity and formation of the reactive trienamine intermediate. The hyperhomodesmotic equations used to assess the energy penalty for dearomatization show that the formation of the iminium ion decreases the energy cost for dearomatization, especially when X = O and S. Furthermore, we also investigated the role that the catalyst and heteroatom may have on the orbital coefficients of the various positions of the trienamine intermediary in order to better understand and/or predict the regioselectivity these systems may showcase. Synergistic effects between the catalyst and the heteroatom of the aromatic ring were observed to increase electron density at the most remote positions of several of the model systems studied.
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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 | 0.001 | 0.001 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| 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) | 0.000 | 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".