Nickel‐Catalyzed <i>P</i> ‐Arylation of HP(= O)(R/OR) <sub>2</sub> Nucleophiles with (Hetero)Aryl Chlorides Enabled by DalPhos Ligation
Bibliographic record
Abstract
Abstract Herein we disclose our development of broadly useful C‐P cross‐couplings of (hetero)aryl chlorides and HP(O)(R) 2 or HP(O)(OR) 2 nucleophiles, enabled by use of nickel/DalPhos‐based catalysts. These typically use 5 mol% nickel at 110 °C for 18 hours, but the feasibility of shorter or milder reactions was demonstrated with one specific example. The ability to apply such transformations on gram scale, and in the P ‐arylation of active pharmaceutical ingredients (APIs) (i.e., chloroquine and clozapine) was also shown. Also described are our findings arising from the computational modelling of such cross‐coupling reactions by use of density functional theory (DFT) calculations, which confirmed the clear preference for C‐P bond formation involving three‐centered reductive elimination through substrate P V pathways.
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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) | 0.000 | 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 | 0.000 |
| Insufficient payload (model declined to judge) | 0.002 | 0.001 |
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".