Dearomative dimerization of quinolines and their skeletal rearrangement to indoles triggered by single-electron transfer
Bibliographic record
Abstract
Dearomatization of two-dimensional (2D) planar aromatic feedstocks enables the introduction of three-dimensional (3D) vectors to new molecular scaffolds, vastly expanding the chemical space for drug discovery. Here, we demonstrate that photoinduced single-electron reduction of quinolines under polysulfide anion photocatalysis triggers dearomative dimerization and an unprecedented skeletal rearrangement. In the presence of excess formate as the stoichiometric reductant, a complex polyheterocyclic hybrid of a 2,5-methanobenzo[b]azepine and a tetrahydroisoquinoline is formed in a net-reductive manner, whereas in the presence of a trialkylamine instead of formate, sequential dimerization and skeletal rearrangement occurs to afford 4-(3-indolylmethyl)quinolines in a redox-neutral manner. The remarkable way in which the additive dictates the reaction course showcases the unique tunability of polysulfide anion mediated redox photocatalysis. These observations enabled the design of a net-reductive skeletal rearrangement of 4-arylquinolines to 3-(arylmethyl)indoles. Detailed mechanistic investigations reveal that this umpolung transformation from electron-deficient quinolines to electron-rich indoles is mediated via a 1,2-aryl migration/ring-contraction sequence, as opposed to the more commonly invoked neophyl-like rearrangement.
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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 | 0.000 |
| 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 | 0.000 | 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".