Hydrosilylative Reduction of Tertiary Amides to Amines Catalyzed by <i>N</i>‐(Phosphinoaryl)anilido Complexes of Iron and Cobalt
Bibliographic record
Abstract
Abstract The synthesis and structural characterization of low‐coordinate Fe(II) and Co(II) complexes supported by the monoanionic P,N‐ligand N ‐(2‐dicyclohexylphosphinophenyl)‐2,6‐diisopropylanilide are described. A three‐coordinate (P,N)Fe‐hexamethyldisilazide complex ( 2 ), and four‐coordinate (P,N)Fe‐ ( 3‐Fe ) and (P,N)Co‐alkyl ( 3‐Co ) complexes were evaluated as pre‐catalysts for the hydrosilylative reduction of amides with PhSiH 3 (5 mol % pre‐catalyst, 1 equiv. PhSiH 3 , 80 °C, 1–24 h). The Fe complex 2 proved to be more broadly effective for the reduction of a variety of tertiary amide substrates, and was shown to mediate the reduction of N , N ‐dibenzylbenzamide at a loading of 1 mol %, to achieve near quantitative formation of tribenzylamine in 1 h (80 °C). Complex 2 also proved effective for the hydrosilylation of tertiary amides under ambient conditions (5 mol % Fe, 24 h), which is a unique example of room temperature amide hydrosilylation mediated by an Fe catalyst without the need for photochemical activation. Given the widespread use of amide reduction protocols in synthesis, the development of efficient Fe‐based catalysts that operate under mild conditions is an important target.
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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 | 0.000 |
| 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".