Hypervalent iodine-mediated oxidative alkene arylation: a thorough analysis
Bibliographic record
Abstract
A hypervalent iodine (HVI)-mediated, oxidative alkene arylation reaction has been developed. Both Koser’s reagent (PhI(OH)OTs) and (diacetoxyiodo)toluene (TolI(OAc)2) were equally viable as oxidants, which reacted with ortho-vinylbiphenyl derivatives to produce tri-, tetra-, and pentacyclic polycyclic aromatic hydrocarbons in yields up to 97%. Comparison of this stoichiometric reaction with a previously reported catalytic process showed that these protocols were largely complementary, and that they likely operate via the same general mechanistic sequence involving vinyliodonium salts decomposing into vinylene phenonium ions. Various mechanistic control experiments were conducted, which ruled out epoxides as intermediates, and which showed that E- and Z-alkene geometry in 10-substituted ortho-vinylbiphenyls had no impact on the ensuing isomeric product distributions. These experiments strongly supported the formation of E-vinyliodonium ions as initial reaction intermediates, and while the occurrence of 1,2-phenyl shift products was a common phenomenon, we concluded that alkyl substitution on the ortho-vinylbiphenyl was a requirement for this alternate pathway to occur.
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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) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.001 | 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".