Exploring the utility of a new chiral phosphoramidite <i>P</i>,<i>N</i>-ligand derived from (<i>R</i>)-BINOL and 7-azaindole in asymmetric catalysis
Bibliographic record
Abstract
Lithiation of 7-azaindole, followed by quenching with [(R)-(1,1′-binaphthalene-2,2′-diyl)]chlorophosphite afforded the new chiral phosphoramidite 1 in 92% isolated yield. Treatment of 0.5 equiv. of [(COD)MCl] 2 (M = Rh, Ir; COD = η 4 -1,5-cyclooctadiene) with 2 equiv. of 1 afforded the corresponding [(κ 1 -P,N-1)(κ 2 -P,N-1)MCl] complexes in 68% (2a, Rh) and 72% (2b, Ir) yield, while treatment of (PPh 3 ) 3 RhCl with 1 equiv. of 1 afforded [(PPh 3 )(κ 2 -P,N-1)RhCl] (3) as an analytically pure solid in 74% isolated yield. In examining the reaction of 1 with a mixture of 0.5 equiv. of [(COD)RhCl] 2 and 1 equiv. of AgBF 4 , an inseparable mixture of [(κ 2 -P,N-1) 2 Rh] + BF 4 – (4a) and [(COD)(κ 2 -P,N-1)Rh] + BF 4 – (5a) was generated. Under analogous conditions employing [(COD)IrCl] 2 , the complex [(COD)(κ 2 -P,N-1)Ir] + BF 4 – (5b) was obtained in 86% isolated yield. Treatment of 0.5 equiv. of [(η 3 -allyl)PdCl] 2 with 1 afforded [(η 3 -allyl)(κ 2 -P,N-1)Pd] + Cl – (6) in 86% isolated yield. The application of 1 in platinum group metal-mediated asymmetric chemical transformations, including alkene hydrogenation and hydroboration, ketone hydrosilylation, and allylic alkylation, was examined.Key words: chiral, ligand, phosphoramidite, asymmetric catalysis.
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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) | 0.000 | 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".