Manganese‐Ketenimine Intermediates as Active Catalysts in the Michael Addition of Unactivated Nitriles to α,β‐Unsaturated Ketones
Bibliographic record
Abstract
Abstract The Michael addition of unactivated nitriles to α,β‐unsaturated ketones is a challenging yet desirable strategy for installing alkyl cyano‐groups (R‐CN) in organic molecules. However, despite formidable efforts, using acetonitrile as a Michael donor in these reactions has remained a significant challenge. Herein, we report a highly active manganese(I) complex [(PC NHC P)Mn(CO) 2 H] ( 1 ), which chemoselectively catalyzes the 1,4‐addition of unactivated nitriles (incl. acetonitrile) to α,β‐unsaturated ketones. The developed methodology operates under mild conditions, does not require any additives or bases, features low catalyst loadings (1 mol %), fast reaction times (2–8 hours), and is compatible with a wide variety of functional groups, including halides, trifluoromethyl, alkenyl, alkynyl, and (hetero)aryl groups. Extensive mechanistic studies revealed that after base‐free activation of the nitrile, either the N‐bound manganese‐ketenimine (propionitrile or benzyl cyanide) or the C‐bound manganese‐cyanoalkyl (acetonitrile) complex is formed. The difference in stability of these two species explains why more sterically hindered and presumably less activated nitriles ( i.e ., propionitrile, and butyronitrile) show higher reactivity than their corresponding more activated congeners ( i.e ., acetonitrile). Finally, the practicality of our approach was demonstrated through a gram‐scale reaction and subsequent derivatizations of the obtained product into important organic motifs such as ene‐lactams and tetrahydropyridines.
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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 | 0.001 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.001 | 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) | 0.001 | 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 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".