Concerning the Structures of Alkali-Metal-Mediated<i>ortho</i>Zincation of Benzamides and Phenyl<i>O</i>-Carbamate
Bibliographic record
Abstract
As a further contribution to alkali-metal-mediated metalation, a method for converting C−H bonds directly to C−Zn bonds without the need for an additional salt metathesis step, reactions of the sodium TMP-zincate [(TMEDA)Na(μ-TMP)(μ- t Bu)Zn( t Bu)] ( 1 ) with three different electron-rich aromatic substrates, have been investigated. Under ambient-temperature conditions, N, N -diethylbenzamide, N, N -diethyl-3-methoxybenzamide, and N, N -diethyl phenyl O -carbamate were zincated ortho to the substituent group (in between both substituents in the second case) in the crystalline products [(TMEDA)Na(μ-TMP){μ-2-[1-C(O)NEt 2 ]C 6 H 4 }Zn( t Bu)] ( 3 ), [(TMEDA)Na(μ-TMP){μ-2-(1-C(O)NEt 2 )(3-OMe)C 6 H 3 }Zn( t Bu)] ( 4 ), and [(TMEDA)Na(μ-TMP){μ-2-(1-OC(O)NEt 2 )C 6 H 4 }Zn( t Bu)] ( 6 ). X-ray crystallography established that, in each case, the deprotonated aromatic fragment is captured by the residue of the bimetallic base, giving rise to seven-membered (NaNZnCCCO) ring structures for 3 and 4 and an eight-membered (NaNZnCCOCO) ring structure for 6 . The new zincated aromatics were also characterized by solution-state 1 H and 13 C NMR spectroscopy. Reactivity studies of 3, 4, and 6 were also performed with iodine. In each case, three molar equivalents of iodine in THF solution gave the ortho -iodo products N, N -diethyl-2-iodobenzamide ( 7 ), N, N -diethyl-2-iodo-3-methoxybenzamide ( 8 ), and N, N -diethyl-2-iodophenyl- O -carbamate ( 9 ) in quantitative, 71% and 75% yields as determined by NMR analysis, respectively.
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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 | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.001 |
| 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 | 0.000 |
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".