Comparative Study of the Reactivity of Brook and Couret Silenes: Aldehyde Addition
Bibliographic record
Abstract
The addition of the mechanistic probe trans -2-phenylcyclopropanecarbaldehyde ( 10 ) to the naturally polarized Couret silene Mes 2 Si C(H)(CH 2 -t -Bu) ( 2 ) and the relatively nonpolar Brook silenes (Me 3 Si) 2 Si C(R)(OSiMe 3 ), where R = t -Bu ( 1a ), 1-Ad ( 1b ), respectively, was examined. The addition of aldehyde 10 to silene 2 produces vinylsilane 17, siloxetanes 18a − c, and ester 19 . Upon chromatography, siloxetanes 18a − c were found to undergo conversion to the alkenes trans - 20 and cis - 20 and (Mes 2 SiO) 2 . The formation of siloxetanes 18a − c and ester 19 is consistent with the formation of a 1,4-zwitterionic intermediate during the course of the addition of the aldehyde to silene 2 . The addition of the cyclopropyl aldehyde 10 to Brook silenes produces the cis,trans -dienes 23 and 26, siloxetanes 24a, b and 27a, b, and acylsilanes 25a, b and 28a, b derived from silenes 1a and 1b, respectively. The formation of the cis,trans -dienes and the siloxetanes provides compelling evidence for the formation of an α-cyclopropylcarbinyl radical during the course of the addition of the aldehyde to the Brook silenes. This work provides a unique comparison of the reactivities of the naturally polarized Couret silene 2 and the relatively nonpolar Brook silenes 1a, b toward aldehydes. It is evident from the results that the polarity of the Si C bond of the silene has a profound influence on the mechanism of the addition of aldehydes to silenes.
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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) | 0.002 | 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".