Intramolecular hydroamination of unactivated alkenes with secondary alkylamines catalyzed by iridium phosphino–phenolate complexes
Bibliographic record
Abstract
The phosphino–phenolate complex (κ 2 -{2-i-Pr 2 PC 6 H 4 }O)Ir(COD) (COD = η 4 -1,5-cyclooctadiene; 1) is shown to be an effective precatalyst for the intramolecular hydroamination of unactivated alkenes with pendant secondary alkylamines, providing either pyrrolidine or piperidine heterocycles in high isolated yields. While monitoring the progress of a selected test reaction of this type, a significant induction period (~3 h) was observed; variable-temperature 1 H and 31 P NMR studies (25–100 °C) under catalytically relevant conditions revealed no new metal-containing species. In an effort to develop an enantiopure variant of 1, a synthetic route to the chiral (κ 2 -P,O)Ir(COD) complex (7), which features a 1-aryl-2,5-dialkylphospholane structure derived from (2S,5S)-2,5-hexanediol cyclic sulfate, was developed. The structure of 7 was confirmed by use of single-crystal X-ray diffraction techniques. While 7 failed to provide enantioselectivity in the intramolecular hydroamination of unactivated alkenes with pendant secondary alkylamines, the activity of 7 was found to be comparable to that of 1.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.002 | 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".