Sakurai Addition and Ring Annulation of Allylsilanes with α,β-Unsaturated Esters. Experimental Results and ab Initio Theoretical Predictions Examining Allylsilane Reactivity
Bibliographic record
Abstract
Trimethylallylsilane has been shown to add to methyl acrylate in good yield when catalyzed by TiCl(4) at room-temperature despite literature reporting to the contrary. Further, even with these small alkyl ligands on the metal, ring annulation occurs to a large extent, in addition to simple allylation (Sakurai addition). The kinetic product is the ((trimethylsilyl)methyl)cyclobutane derivative which can be isomerized to cyclopentanoid, the thermodynamic product, if left in the presence of the catalyst. Consistent with other literature in this area, increasing the size of the ligands on silicon increases both the rate of product formation and the proportion of ring annulation relative to allylation. To develop a predictive model for allylsilane reactivity, ab initio gas-phase calculations have been made on the parent allylsilane with different ligands on the metal and on the reaction between these allylsilanes and acrolein, acrylic acid, and methyl acrylate. Predictions indicate that as the length of n-alkyl ligands on silicon increase, so does the apparent ability of the Si-Calpha bond of the allylsilane to hyperconjugate with developing vacant p orbital on Cbeta as the allylsilane begins to attack an electrophile. This is corroborated by a gradually increasing HOMO in the ground-state allylsilane as the ligands are changed from methyl through to n-hexyl and an increasing Si-Calpha bond length and decreasing Si-Calpha-Cbeta bond angle in the protonated species. These results in the gas phase mirror the reactivity of these n-alkyl-substituted allylsilanes in experiment; i.e., as the length of the alkyl chain increases, reactivity increases significantly. Triisopropylallylsilane, a very reactive silane, appears to anomalous in charge distribution and geometrical features compared with other substituted allylsilane systems which is due, presumably, to steric effects. The calculations on the protonated species would indicate that almost no hyperconjugative stabilization can occur on the basis of the bond lengths and angles necessary to promote good orbital overlap between the Si-Calpha bond and the empty p orbital on Cbeta. However, the gas-phase reaction of the triisopropylallylsilane with acrolein and methyl acrylate led to comparatively low energy barriers of 13.1 and 24.5, respectively, which is consistent with its high experimental reactivity. Together, this computational analysis has produced a useful model for predicting allylsilane reactivity and some possible explanations for this reactivity.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| 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) | 0.003 | 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 source (direct Gemma or distilled Codex), 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".